Note: Descriptions are shown in the official language in which they were submitted.
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EMISSIVE MULTICHROMOPHORIC SYSTEMS
FIELD OF THE INVENTION
This invention relates to synthetic multichromophoric systems that preferably
exhibit:
(i) low energy emissive excited states in which the transition dipoles of the
constituent
pigment building blocks are correlated in defined phase relationships, (ii)
excited state
polarization over long timescales, (iii) emission quantum yields that have an
unusual
dependence upon supramolecular structure and emission wavelength, (iv)
collective oscillator
behavior in their respective electrochemically excited states, and (v)
integrated emission
oscillator strengths that are large with respect to that manifest by the
benchmark monomeric
chromophore.
BACKGROUND OF THE INVENTION
The desire to enhance superradiant emission and electroluminescence in
processable
materials has generated considerable interest in the photophysical properties
of broad classes
of conjugated oligomers and polymers. (See, e.g., U.S. Pat. No. 5,798,306,
which is
incorporated by reference). Interestingly, these technologically important
electrooptic
proprties appear to be connected, in that they both derive from long-range
electronic
excitations (one-dimensional excitons) that extend over multiple monomer
units. Although
electroluminescence in conjugated polymers has been a subject of long-standing
interest,
detailed examination of the superradiant properties of these materials has
come to the fore
only recently, fueled by the observation that amplification of stimulated
emission (ASE)
results when thin films of superradiant polymers are optically pumped at high
intensity.
Superradiance is an example of cooperative emission that originates when an
ensemble of emitters (emissive pigment blocks) is excited into a correlated
state that
possesses a macroscopic dipole moment. One key hallmark of this optical,
nonlinear
phenomenon is the emission of a coherent radiation pulse with a peak intensity
proportional
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to the square of the number of correlated emitters. Supperradiant pigment
arrays thus
manifest radiative rate constants k, that exceed that determined for their
respective
monomeric chromophoric building blocks, a dependence highlighted in the
Einstein equation
for spontaneous emission (eq 1 ),
__
kr 3s6hc3 L Er JE3Kf~~2 (1)
where E is the emission energy, n and s are respectively the medium's
refractive index and
dielectric strength, and (~) is the emission transition dipole moment. Note
that the magnitude
of kr is a signature of the number of coupled oscillators; hence, for an
assembly of m
pigments exhibiting superradiant emission, the classically predicted, maximal
value of k,. that
could be observed corresponds to m times the radiative rate constant
determined for the
corresponding monomeric chromophore.
In one aspect of the present invention, the monomeric chromophoric building
blocks
are conjugated to form dimers, trimers, oligomers or polymers. The monomeric
chromophoric building blocks can, for example, be porphyrins. Those in the art
will
recognize that porphyrins are derivatives of porphine, a conjugated cyclic
structure of four
pyrrole rings linked through their 2- and 5-positions by methine bridges.
Porphyrins can
bear up to 12 substituents at meso (i.e. a) and pyrrolic (i.e.,(3) positions
thereof. (See, e.g.,
U.S. Pat. No. 5,371,199, 5,783,306, and 5,986,090 which are incorporated by
reference)
Porphyrins can be covalently attached to other molecules. The electronic
features of the
porphyrin ring system can be altered by the attachment of one or more
substituents. The term
"porphyrin" includes derivatives wherein a metal atom is inserted into the
ring system, as
well as molecular systems in which ligands are attached to the metal. The
substituents, as
well as the overall porphyrin structure, can be neutral, positively charged,
or negatively
charged.
Numerous porphyrins have been isolated from natural sources. Notable porphyrin-
containing natural products include hemoglobin, the chlorophylls, and vitamin
B 12. Also,
many porphyrins have been synthesized in the laboratory, typically through
condensation of
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suitably substituted pyrroles and aldehydes. However, reactions of this type
generally proceed
in low yield, and cannot be used to produce many types of substituted
porphyrins.
SUMMARY OF THE INVENTION
In one aspect, the present invention conjugated multichromophoric systems
including a polymer comprising a plurality of linked porphyrinic monomer units
having
formula ( l ), (2), or (3):
R (1)
Ra2
"'
Res
Ret /~~ R84
~\
N~
N
RA4 ~ RA2
H
H
~
N
N
Res
R87
RA3
R86
R (2)
R
A
~
R
B2
BS
RBt /~~ RBA
~\
N\
/N
R A a /N~ R A 2
N
N
R ~ R
ea \ es
~
RB7
RA3
R86
3)
R
RB3
RB t / RB4
~~
~\
/
N
N
\
M'
R R
A1 N A2
N
~N
Rgg \ RSS
~
'
RB7
RA3
R~6
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wherein M and M' are metal atoms and RA,-RA4 and RB,-RB$ are, independently, H
or
chemical functional groups that can bear a negative charge prior to attachment
to a porphyrin
coumpound. In certain embodiments, at least one of RA,-RA4 has formula CH=CH2
or at
least one of RA,-RA4 or RB,-RB8 has formula C(RC)=C(RD)(RE), provided that at
least one
of RC, RD, and RE is not H, where RC , RD, and RE are, independently, H, F,
Cl, Br, I, alkyl
or heteroalkyl having from 1 to about 20 carbon atoms, aryl or heteroaryl
having about 4 to
about 20 carbon atoms, alkenyl or heteroalkenyl having from 1 to about 20
carbon atoms,
alkynyl or heteroalkynyl having from 1 to about 20 carbon atoms, trialkylsilyl
or
porphyrinato; M is a transition metal, a lanthanide, actinide, rare earth or
alkaline metal. RC ,
RD, and RE also can include peptides, nucleosides, and/or saccharides.
In other embodiments, at least one of RA,-RA4 or RB,-RBg has formula C=C(RD).
In
further preferred embodiments, at least one of RA,-RAQ is haloalkyl having
from 1 to about 20
carbon atoms. In further preferred embodiments, at least one of RB,-RBg is
haloalkyl having 2
to about 20 carbon atoms or at least at least five of Rg,-Rgg are haloalkyl
having from 1 to
about 20 carbon atoms or haloaryl having from about 6 to about 20 carbon
atoms. In further
preferred embodiments, at least one of RB,-RBg is haloaryl or haloheteroaryl
having about 4
to about 20 carbon atoms. In still further preferred embodiments, at least one
of RA,-RA4 or
RB,-RBg includes an amino acid, peptide, nucleoside, or saccharide.
The present invention also provides processes and intermediates for preparing
substituted porphyrins. In certain embodiments, the processes comprise
providing a
porphyrin compound having formula (1), (2), or (3) wherein at least one of RA,
-RA4 or RB,-
RBg is a halogen and contacting the porphyrin compound with a complex having
formula
Y(L)2 wherein Y is a metal and L is a ligand. This produces a first reaction
product, which is
contacted with an organometallic compound having general formula T(RL)Z(RD),
T(RL)Z(Rp)y (XB ) w , T(Rp)(XB ) or T(Rp) y where T is a metal; XB is a
halogen; RL is
cyclopentadienyl or aryl having about 6 to about 20 carbon atoms; Rp is alkyl
having 1 to
about 10 carbon atoms, alkenyl or alkynyl having 2 to about 10 carbon atoms,
aryl having
about 6 to about 20 carbon atoms; z and w are greater than or equal to 0; and
y is at least 1.
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This contacting produces a second reaction product which, through reductive
elimination,
yields a third reaction product that contains a porphyrin substituted with Rp.
In another aspect, the invention provides polymers comprising linked porphyrin
units.
In certain embodiments, porphyrin units having formula ( 1 ), (2), or (3)
share covalent bonds.
In other embodiments at least one of RA,-RA4 or Rg,-RB8 function as linking
groups. In these
embodiments, at least a portion of a linking group can have formula
[C(RC)=C(RD)(Rg)]X ,
[C=C(RD)]x , [CH2(RC)-CH(RD)(Rg)]x or [CH=CH(RD)]x where x is at least 1. The
remaining of RA,-RA4 and Rg,-RBg can be H, halogen, alkyl or heteroalkyl
having 1 to about
20 carbon atoms or aryl or heteroaryl having 4 to about 20 carbon atoms,
C(RC)=C(RD)(RE),
C=C(RD), or a chemical functional group that includes a peptide, nucleoside,
and/or
saccharide. In other preferred embodiments, the linking group is cycloalkyl or
aryl having
about 6 to about 22 carbon atoms.
The invention also provides processes for preparing porphyrin-containing
polymers.
In certain embodiments, the processes comprise providing at least two
compounds that,
independently, have formula (1), (2) or (3) wherein at least one of R,q,-RA4
or RB,-RB8 in
each of the compounds contains an olefmic carbon-carbon double bond or a
chemical
functional group reactive therewith. In other embodiments, at least one of RA,-
RA4 or RB,-
RB$ in each of the compounds contains a carbon-carbon triple bond or a
chemical functional
group reactive therewith. The compounds are then contacted for a time and
under reaction
conditions effective to form covalent bonds through the carbon-carbon double
and/or triple
bonds.
In another aspect of the invention, emissive pigment building blocks such as
porphyrin monomer units that, independently, have formula (1), (2), or (3),
are linked to form
a conjugated dimer, trimer, oligomer, polymer, or other highly conjugated
synthetic
multichromophoric systems that exhibits low energy fluorescent excited states
in which the
transition dipoles of the pigment building blocks are correlated in defined
phase relationships.
Analyses of corresponding fluorescence intrinsic decay rate and quantum yield
data show
that, in another embodiment, ethyne- and butadiyne-bridged multiporphyrin
species that
manifest high excited-state anisotropies display exceptionally large emitting
dipole strengths,
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establishing a new precedent for superradiant oligopigment assemblies. This
photophysical
behavior derives not only from the fact that these conjugated pigment arrays
behave as
collective oscillators; the large transition dipole moment of the porphyrinic
monomer unit
combined with strong chromophore-chromophore electronic coupling ensure large
Frank-
Condon barriers for intersystem crossing between their respective S, and T,
states. These
results indicate that substantial emitting dipole strengths can in fact be
realized for low energy
fluorescing chromophores, and that simple energy gap law considerations do not
preclude the
design of high quantum yield near IR emitters.
In another aspect, the present invention provides methods comprising the steps
of
providing a conjugated compound comprising at least two covalently bound
moieties and
then exposing the compound to an energy source for a time and under conditions
effective to
cause it to emit light that has a wavelength of 650-2000 nm and is of an
intensity that is
greater than a sum of light individually emitted by the component moieties. In
preferred
embodiments emission from said materials can be effected by optical or
electrical pumping.
For example, when these materials are optically pumped, evaluation of the
emission dipole
strength can be made from determination of the emission quantum yield and the
corresponding emission decay rate using conventional methods [see for example:
Lakowicz,
J. R Principles of Fluorescence Spectroscopy (Plenum Press, New York, 1983);
Turro, N. J.
Modern Molecular Photochemistry (The Benjamin/Cummings Publishing Co., Ine.,
Menlo
Park, 1978); Dexter, D. L. J. Chem. Phys. 21, 836-850 (1953); Dicke, R. H.
Phys. Rev. 93, 99
(1954)].
For example, the fluorescence quantum yield (QY) can be determined by the
reference
method[Lakowicz, 1983], using the above relation where JI~o~nplex and
JIs~~ndard are the
respective, total integrated fluorescence intensities of the complex and
emission standard,
A~o",P,eX and As,a~aaa are the corresponding wavelength-specific absorbances,
and QYstandard 1S
the accepted fluorescence QY value for the standard chromophore. The quantity
(no~o~nP~ex~nos~anaaa)2 represents the solvent refractive index correction.
Steady state emission
spectra can be obtained on a conventional luminescence spectrometer having the
appropriate
emission detectors. Sample concentrations are adjusted typically such that the
absorbance is
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between 0.005 and 0.04 at the excitation wavelength. Emission spectra obtained
for the
chromophore (fluorophore, phosphore, or lumophore) are corrected to account
for the
wavelength-dependent efficiency of the detection system which can be
determined using the
spectral output of a calibrated light source obtained from the National Bureau
of Standards.
Secondary corrections to the emission spectra used to determine QYs (such as
energy-
dependent intensity corrections necessitated by the variable band
pass/constant wavelength
resolution data acquisition mode of the grating monochromator) are performed
as outlined by
Lakowicz[Lakowicz, 1983]. Quantum yields are determined typically using two
standard
benchmarks for each chromophore.
Emitting dipole strengths are defined a5 <'.I~~hromophore/<~reference~ where
<'.l~,efcrcnce
corresponds to the emission dipole strength of one of the covalently bound
moieties that
defines the conjugated compound. <~ values can be determined from the Einstein
equation
for spontaneous emission, when the radiative rate constant k,. has been
determined from
appropriate time-resolved spectroscopic techniques [Lakowicz, J. R. Principles
of
Fluorescence Spectroscopy (Plenum Press, New York, 1983); Turro, N. J. Modern
Molecular
Photochemistry (The Benjamin/Cummings Publishing Co., Inc., Menlo Park, 1978);
Dexter,
D. L. J. Chem. Phys. 21, 836-850 (1953); Dicke, R. H. Phys. Rev. 93, 99
(1954)].
In certain embodiments, the compound exhibits an integral emission oscillator
strength that is greater than a sum of emission oscillator strengths exhibited
by its component
moieties. Representative moieties are those that include a conjugated ring
system.
Preferably, at least one of the moieties is a laser dye, fluorophore,
lumophore, or phosphore.
Particularly preferred moieties include porphyrins, porphycenes, rubyrins,
rosarins,
hexaphyrins, sapphyrins, chlorophyls, chlorins, phthalocyanines,
porphyrazines,
bacteriochlorophyls, pheophytins, texaphyrins, and their corresponding
metalated derivatives.
Another class of representative moieties are conjugated macrocycles comprising
16 or more
carbon atoms and four or more heteroatoms such as N, O, S, Se, Te, B, P, As,
Sb, Si, Ge, Sn,
and Bi.
The moieties preferably are bound by at least one carbon-carbon double bond,
carbon-
carbon triple bond, a combination thereof, or an imine, phenylene, thiophene,
amide, ether,
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thioether, ester, ketone, sulfone, or carbodiimide group. Representative bond
types include
ethynyl, ethenyl, allenyl, butadiynyl, polyvinyl, polyynyl, thiophenyl,
furanyl, pyrrolyl, p-
diethynylarenyl bonds and any conjugated hetrocycle that bears diethynyl,
di(polyynynyl),
divinyl, di(polyvinvyl), or di(thiophenyl) substituents. Such materials thus
include, laser
dyes, fluorophores, lumophores, and/or phosphore that are covalently bound
with, for
example, alkynyl or alkenyl bonds.
The conjugated synthetic multichromophoric systems of the invention can be
used, for
example, as dyes, catalysts, contrast agents, antitumor agents, antiviral
agents,
electroluminescent materials, LEDs, lasers, photorefractive materials and in
chemical sensors
and electrooptical devices. Thus, in one aspect, the present invention
provides lasers in
which a dye solution is disposed in a resonant cavity and comprises a compound
of the
invention and an aqueous or non-aqueous solvent that is substantially unable
to chemically
react with said compound and to absorb and emit light at a wavelength at which
said
compound absorbs and emits light. Lasers according to the invention further
include a
pumping energy source that produces stimulated emission in the dye solution.
Further lasers according to the invention are those that include a solid body
that, in
turn, includes a compound of the invention and a host polymer that is unable
to chemically
react with the compound and unable to absorb and emit light at a wavelength at
which the
compound absorbs and emits light. Such lasers further include an energy source
that either is
coupled with the solid body and generates light in the solid body, or is
coupled with the host
polymer and generates light therein. Also, an optical amplifier comprising a
polymeric
optical waveguide and a compound of the invention is provided.
The present invention also provides polymer grids comprising a body of
electrically
conducting organic polymer. Such a body has an open and porous network
morphology and
defines an expanded surface, area void-defining porous network. An active
electronic
material comprising a compound of the invention is located within at least a
portion of the
void spaces defined by the porous network. The conducting organic polymer may
also
include a compound of the invention.
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The present invention also provides polymer grid electrodes comprising a body
of
electrically conducting organic polymer that is electrically joined to an
electrical connector.
The body should have an open and porous network morphology and define an
expanded
surface area, void-defining porous network, with an active electronic material
comprising a
compound of the invention located within at least a portion of the void spaces
defined by the
porous network.
The invention also provides solid state polymer grid triodes comprising a
first
electrode and a second electrode spaced apart from one another with a polymer
grid
comprising a body of electrically conducting organic polymer that includes a
compound of
the invention. The body preferably has an open and porous network morphology
and defines
an expanded surface area void-defining porous network interposed between the
first electrode
and the second electrode.
In another aspect, the present invention provides light-emitting polymer grid
triodes
comprising a first electrode and a second electrode spaced apart from one
another with a
polymer grid comprising a body of electrically conducting organic polymer. The
body in
such a triode has an open and porous network morphology and defines an
expanded surface
area, void-defining porous network interposed between the first and second
electrodes. An
active luminescent semiconducting electronic material comprising a compound of
the
invention is interposed between the first and second electrodes, and serves to
transport
electronic charge carriers between the first and second electrodes, the
carriers being affected
by the polymer grid such that on applying a turn-on voltage between the first
and second
electrodes, charge carriers are injected and light is emitted.
The present invention also relates to light-responsive diode systems
comprising a
diode that, in turn, includes: a conducting first layer having high work
function; a
semiconducting second layer in contact with the first layer, the second layer
made comprising
a compound of the invention; and a conducting third layer in contact with the
second layer.
Systems according to the invention further include a source for applying a
reverse bias across
the diode, a source for impinging light upon the diode, and a source for
detecting an electrical
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current produced by the diode when the reverse bias is applied to the diode
and light is
impinged upon the diode.
The present invention also provides light-responsive diode systems that
comprise a
diode that itself includes: a conducting first layer having high work
function; a
semiconducting second layer in contact with the first layer, the second layer
made comprising
a compound of the invention; and a conducting third layer in contact with the
second layer,
the third layer comprising an inorganic semiconductor doped to give rise to a
conductive
state. Such systems further include a source for applying a reverse bias
across the diode, a
source for impinging light upon the diode, and a source for detecting an
electrical current
produced by the diode when the reverse bias is applied to the diode and light
is impinged
upon the diode.
Also provided are dual function light-emitting, light responsive input-output
diode
systems comprising a diode having a conducting first layer having high work
function, a
semiconducting second layer in contact with the first layer comprising a
compound of the
invention, and a conducting third layer in contact with the second layer. Such
systems further
comprise a source for applying a reverse bias across the diode, a source for
impinging light
upon the diode, and a source for detecting an electrical current produced by
the diode when
the reverse bias is applied to the diode and light is impinged upon the diode.
The present invention also provides dual function light-emitting, light
responsive
input-output diode systems comprising a diode having a conducting first layer
having high
work function, a semiconducting second layer in contact with the first layer
that comprises a
compound of the invention, and a conducting third layer in contact with the
second layer.
Such systems further include a source for applying a reverse bias across the
diode, a source
for impinging an input signal or light upon the diode, a source for detecting
an electrical
current produced by the diode when the reverse bias is applied to the input
signal of light is
impinged upon the diode, a source for halting the applying of reverse bias,
and a source for
applying a positive bias output signal across the diode, the positive bias
output signal being
adequate to cause the diode to emit an output signal of light.
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The invention also provides dual function input-output processes comprising
the steps
of applying a reverse bias across the diode and impinging an input signal of
light upon the
diode, detecting as an electrical input signal an electrical current or
voltage produced by the
diode when the reverse bias is applied to the diode and the input signal of
light is impinged
upon the diode, halting the applying of reverse bias, and applying a positive
bias output signal
across the diode, the positive bias output signal being adequate to cause the
diode to emit an
output signal of light in response thereto.
Also provided are articles comprising a unitary solid state source of
electromagnetic
radiation, in which the source has a layer structure that comprises a
multiplicity of layers,
including two spaced apart conductor layers with compound of the invention
therebetween,
and further comprising contacts for causing an electrical current to flow
between the
conductor layers, such that incoherent, electromagnetic radiation of a first
wavelength is
emitted from the compound of the invention. The layer structure preferably
comprises an
optical waveguide comprising a first and a second cladding region with a core
region
therebetween, with the optical waveguide disposed such that at least some of
said incoherent
electromagnetic radiation of the first wavelength is received by the optical
waveguide, and
the core region comprises a layer of a second organic material selected to
absorb the
incoherent electromagnetic radiation of the first wavelength, and to emit
coherent
electromagnetic radiation of a second wavelength, longer than the first
wavelength, in
response to the absorbed incoherent electromagnetic radiation.
The present invention also provides methods for screening compounds. In
preferred
embodiments, such methods comprise the steps of providing a conjugated
compound
comprising at least two covalently bound moieties; exposing the compound to an
energy
source for a time and under conditions effective to cause it to emit light
that has a wavelength
2f of 650-2000 nm; and determining whether or not that emitted light is either
(1) of an intensity
that is greater than a sum of light emitted individually by the moieties or
(2) larger than
emitted by either of the covalently bound moieties.
Also provided are methods in which a compound of the invention is attached to
a
targeting agent which provides localization of the compound in select body
tissues. A probe
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light source can be held external to the tissue to excite the compound into an
emissive state
that has significant emission dipole strength in the 700-1100 nm spectral
domain.
BRIEF DESCRIPTION OF THE FIGURES
The numerous objects and advantage of the present invention can be better
understood
by those skilled in the art by reference to the accompanying figures, in
which:
FIG. 1 shows conjugated porphyrin arrays (compounds 4-12), as well as
electronic absorption spectra thereof. Uncorrected emission spectra are shown
as insets.
Solvent (Compounds 4-10) = CHC13; solvent (compounds 11-12) = 10:1
CHCl3:pyridine.
FIG. 2 shows anisotropic fluorescence dynamics of compounds 4-6. (A)
Comparative time dependent decays for the fluorescence polarized parallel and
perpendicular
to the polarization of the exciting light. (B) Time dependence of the
fluorescence anisotropy.
Excitation (~,ex) and emission (~,em) wavelengths, along with fluorescence
lifetime and
anisotropy depolarization time constants are listed Table 1.
FIG. 3 is a schematic of (A) Potential energy diagram illustrating the
dependence
of the magnitude of electronic state energy separation and the extent of
equilibrium nuclear
displacement (0Q) upon vibrational wave function overlap. (B) Potential energy
diagrams
highlighting the effect of increasing S,-T, nuclear displacement upon the
magnitude of
intersystem crossing rate constants k,sc.
FIG. 4 shows photophysical properties of S1-excited states of
(porphinato)zinc(II)
Complexes 1-12, including (5-ethynyl-10,20-diphenylporphinato)zinc(II)
(Compound 1),
(5,15-diethynyl-10,20-diphenylporphinato)zinc(II) (Compound 2), and (2-ethynyl-
5,10,15,20-
tetraphenylporphinato)zinc(II) (Compound 3): fluorescence lifetime and time-
resolved
anisotropy data.a-d
(a) Samples for transient spectroscopic studies were kept rigorously dry using
standard inert-atmosphere techniques; all data presented were recorded at 293
K in
10:1 CHCI,:pyridine.
(b) The fluorescence lifetimes were determined using a time-correlated single-
photon
counting (TCSPC) apparatus (Regional Laser and Biotechnology Laboratory,
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University of Pennsylvania) that has been described previously; instrument
response
function = 20 ps fwhm. Data were analyzed using the Lifetime (RLBL) program.
Compounds 1-12 exhibit monoexponential decays of the isotropic fluorescence;
the
average evaluated x2 value from fitting of these data for 1-12 was 1.06 ~
0.08.
(c) Time-resolved anisotropy decay data were obtained using rotating
polarization
filters to alternatively select the parallel and the perpendicular components
of the
emission; all other experimental procedures were identical to the lifetime
measurements. Rotational correlation times were calculated using the method
outlined by Wahl, Holtom (Holtom, G. R. Proc. SPIE-Int. Soc. Opt. Eng. 1204, 2-
12
(1990); Wahl, P. Biophys. Chem. 10, 91-104 (1979)). 7~eX and 7~e", denote
respectively
the excitation and emission probe wavelengths. All anisotropy decays could be
fit as
simple monoexponential decay processes, (xz (1-12) = 1.07 ~ 0.05).
(d) zF = fluorescence lifetime; ro = initial fluorescence anisotropy
determined 20 ps
after excitation; it = rotational diffusional time constant.
(e) ro values determined 20 ps after excitation.
(f) Determined by van Grondelle (Monshouwer, R., Abrahamsson, M., van Mourik,
F.
& van Grondelle, R. J. Phys. Chem. B 101, 7241-7248 (1997)).
(g) ro determined 8 ps following excitation for Bchl a, and at zero time for
B820, LH-
2, and LH-1.
FIG. 5 shows Fluorescence Quantum Yield, Stokes Shift, and Calculated
Transition
Dipole Moment Data of Conjugated [(Porphinato)zinc] Complexes 1-12.
(a) The fluorescence quantum yield (QY) of these species was determined by
the reference method, using the relation:
2
f 1 complex A s tan dard ~ n0 complex ) Q
QYcomplex Z Ystandard
f Is tan dard A complex ~nO standard
where ,(I~o~npleX and )Istandard ~'e the respective, total integrated
fluorescence intensities of
the complex and emission standard, A~o,npleX and Astandard are the
corresponding
wavelength-specific absorbances, and QYS"naata is the accepted fluorescence QY
value
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for the standard chromophore. The quantity (n p complexln0 standard)2
represents the
solvent refractive index correction. Steady state fluorescence emission
spectra were
obtained on a Perkin-Elmer LS 50 Luminescence Spectrometer. The concentrations
of all samples were adjusted such that their absorbance was between 0.01 and
0.04 at
the excitation wavelength. All spectra were collected with the single
excitation and
emission monochromators set at 5 nm. Fluorescence spectra obtained for the
(porphinato)zinc(II) complexes as well as the chromophores used as emission
standards were corrected to account for the wavelength-dependent efficiency of
the
detection system which was determined using the spectral output of a
calibrated light
source obtained from the National Bureau of Standards. Secondary corrections
to the
emission spectra used to determine QYs (such as energy-dependent intensity
corrections necessitated by the variable band pass/constant wavelength
resolution data
acquisition mode of the grating monochromator) were performed as outlined by
Lakowicz. Quantum yields were determined using two standard benchmarks for
each
of the conjugated bis- and tris[(porphinato)zinc(II)] complexes.
(Tetraphenylporphinato)zinc(II) (TPPZn) (QY = 0.033, benzene) served as the
reference porphyrinic fluorescence emitter, while a standard laser dye that
featured
significant emission profile overlap with that of the unknown complex served
as a
secondary reference. Benchmark fluorescence emitters utilized were [dye (QY;
solvent; ~,em(nm))]: (i) TPPZn (0.033; benzene; (598, 647)); (ii) TPPZn
(0.028; 10:1
CHCl3:pyridine; (613, 661)); (iii) DODCI (0.44; EtOH; (605)); (iv) HITCI
(0.28;
MeOH (59); (660)); (v) IR-125 (0.13; DMSO; (826)); (vi) DTDCI (0.78; DMSO;
(684)). When TPPZn was used as the standard fluorescence emitter, excitation
of
both the unknown and reference was carried out at either 400 or 428 nm. When
DODCI, HITCI, IR-125, and DTDCI dyes were utilized as emission reference
compounds, ~,eX corresponded to a wavelength within the Q-state manifold of
compounds 1-12. As a check for internal self consistency, the QY for each
emission
standard was experimentally evaluated by the reference method in which another
laser
dye served as the benchmark fluorescence emitter. In all such experiments, the
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computed QY was always within ~ 10% of established literature value,
confirming the
appropriateness of the emission correction factors implemented throughout the
600-
850 nm spectral regime in these experiments. The standard error in quantum
yields
determined by this method is typically taken as ~ 20% of the reported value.
The QY
entries correspond to the average of values obtained from at least three
independent
measurements.
(b) Transition dipole moments were calculated by integrating plots of
extinction coefficient per wavenumber ( sC~~ v ) vs. wavenumber ~~ using the
relation ~2 = (9.188 x 10-3 /n°) f ~~M-'cm-'~~/ u~du where n° is
the refractive
index of the solvent and ,u is the transition dipole moment in Debye. For
these
calculations, the B band region transition dipole moment corresponded to an
integration carried out over the 360 to 520 nm spectral domain, while the
reported Q-
band value derives from an analogous integration over the 520 to 900 nm
wavelength
range.
(c) See R. Monshouwer, M. Abrahamsson, F. van Mourik, R. van Grondelle,
J. Phys. Chem. B 101, 7241-7248 (1997).
FIG. 6 shows Comparative Radiative Lifetimes and Emitting Dipole Strengths of
Conjugated Chromophores 1-12 vs. Benchmark Biological Antennae Systems.
(a) Radiative lifetimes were calculated using the relation i,Q~ = iF/ QY; QY
(fluorescence quantum yield) values utilized were the average of those
reported in
Table II.
(b) Emitting dipole strengths = <l.L~~p~omophore/~~-~~reference~ ~~~ values
were determined
using eq. S; emission energies used in this calculation correspond to the
frequency that
partitions the integrated emission oscillator strength into blue and red
components
having equivalent area. For compounds 1-12, emitting dipole strengths are
referenced
both to TPPZn and an appropriate benchmark ethyne-derivatized
(porphinato)zinc(II)
monomer.
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(c) For meso-to-meso and meso-to-,Q bridged arrays, compound 1 served as the
reference
ethyne-elaborated porphyrin chromophore; ~to-~3 bridged compounds utilized
(porphinato)zinc(II) species 3 as the conjugated pigment reference.
(d) Determined by van Grondelle.
DETAILED DESCRIPTION OF THE INVENTION
Those skilled in the art will recognize the wide variety of dimers, trimers,
oligomers
or polymers that can be prepared from the porphyrin-containing compounds of
the invention.
For instance, somewhat linear polymer chains can be formed wherein a portion
of the
polymer has general formula (PN)r where PN is a porphyrin unit and r is at
least 2. In further
embodiments, linear polymer chains have general formula:
U(QL)L -(PN)s -~h
where QL is a linking group, PN is a porphyrin unit, and h, l, and s are
independently selected
to be at least 1. For example, a portion of such polymers can have formula:
L-(PNOs' -(QLI )l' -(PNZ)s" -(QLZ)l° ~l
wherein PN, and PNZ are independently selected porphyrin units, QL, and QLZ
are
independently selected linking groups, and 1',1", s', and s" are at least 1.
These essentially
linear polymer chains can be cross-linked such that a portion of the polymer
has general
formula:
~-(QH~h -(PN~n -w
wherein QH is a linking group, and h, u, and v are independently selected to
be at least 1. A
portion of these cross-linked polymers can have formula:
U(PN3)u' -(QHOh' -(PN~)u" -(QHz)h' -w
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wherein PN3 is a porphyrin unit, Qty, and Qh2 are independently selected
linking groups,
and h', h", u', and u" are at least 1. Thus, one possible cross-linked polymer
has formula:
~~QL)L~PN)s~~h'
(PN)r'
P
N
(PN)r N
WQL)L~PN)~]h
where r' is at least 1.
The dimers, trimers, oligomers and polymers of the invention are generally
formed by
contacting a substituted porphyrin with a second compound containing
functionality that is
reactive with the functionality contained within the porphyrin. Preferably,
the porphyrin
contains an olefinic carbon-carbon double bond, a carbon-carbon triple bond or
some other
reactive functionality. The contacting should be performed under conditions
effective to form
a covalent bond between the respective reactive functionalities. Preferably,
porphyrin-
containing polymers are formed by metal-mediated cross-coupling of, for
example,
dibrominated porphyrin units. Also, porphyrin-containing polymers can be
synthesized using
known terminal alkyne coupling chemistry. (see, e.g., Patai, et al., The
Chemistry of
Functional Groups, Supplement C, Part 1, pp. 529-534, Wiley, 1983; Cadiot, et
al.,
Acetylenes, pp. 597-647, Marcel Dekker, 1964; and Eglinton, et al., Adv. Org.
Chem., 1963,
4, 225) As will be recognized, the second compound noted above can be a
substituted
porphyrin of the invention or some other moiety such as an acrylate monomer.
Thus, a wide
variety of copolymeric structures can be synthesized with the porphyrins of
the invention.
Through careful substituent selection the porphyrins of the invention can be
incorporated into
virtually any polymeric matrix known in the art, including but not limited to
polyacetylenes,
polyimides, polyacrylates, polyolefins, pohyethers, polyurethanes,
polyquinolines,
polycarbonates, polyanilines, polypyrroles, and polythiophenes. For example,
fluorescent
porphyrins can be incorporated into such polymers as end-capping groups.
The conjugated synthetic multichromophoric systems of the invention can be
used, for
example, as dyes, catalysts, contrast agents, antitumor agents, antiviral
agents, liquid crystals,
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electroluminescent materials, LEDs, lasers, photorefractive materials, in
chemical sensors and
in electrooptical and solar energy conversion devices. They also can be
incorporated into
supramolecular structures. The polymers and supramolecular structures, which
anchor
porphyrin units in a relatively stable geometry, should improve many of the
known uses for
porphyrins and even provide a number of new uses, such as in a solid phase
system for
sterilizing virus-containing solutions, as well as new uses as wave guides,
molecular wires,
optical triggers, and in molecular lasers, optical amplifiers, dye lasers,
polymer grid triodes,
light emitting and light responsive diode systems, LEDs, photovaltaics, as
well as articles
comprising an organic laser, and using the invention in methods and devices
for in vivo
diagnosis detecting IR emission by agents bound to body organs. Representative
uses are
disclosed by, for example, the following patents, which are incorporated
herein by reference:
U.S. Pat. Nos. 5,657,156 (van Veegel, et al.); 5,237,582 (Moses); 5,504,323
(Heeger, et al.);
5,563,424 (Yang, et al.); 5,062,428 (Chance); 5,859,251 (Reinhardt et al.);
5,770,737
(Reinhadt et al.); 5,062,428 (Chance); 5,881,089 (Berggren et al.); 4,895,682
(Ellis, et al.);
4,986,256 (Cohen); 4,668,670 (Rideout, et al.); 3,897,255 (Erickson);
3,899,334 (Erickson);
3,687,863 (Wacher); 4,647,478 (Formanek, et al.); and 4,957,615 (Ushizawa, et
al.). Further
uses are disclosed are disclosed by, for example, U.K. Patent Application
2,225,963 (Casson,
et al.); International Application WO 89/11277 (Dixon, et al.); International
Application WO
91/09631 (Matthews, et al.); International Application WO 98/50989 (Forrest et
al.);
International Application WO 01/49475 (Peumans et al.); European Patent
Application
85105490.8 (Weishaupt, et al.); European Patent Application 90202953.7
(Terrell, et al.);
European Patent Application 89304234.1 (Matsushima, et al.); Lehn, Angew.
Chem. Int. Erl
Engl., 1988, 27, 89; Wasielewski, Chem. Rev., 1992, 92, 435; Mansury, et al.,
J. Chem. Soc.,
Chem. Comm., 1985, 155; Groves, et al., J. Am. Chem. Soc., 1983, 105, 5791;
and Giroud-
Godquin, et al., Angew. Chem. Int. Ed. Engl., 1991, 30, 375. It is believed
that the porphyrins
of the invention can be substituted for the porphyrins disclosed in each of
the foregoing
publications.
A flurophore according to the invention is an emissive compound in which the
spin
multiplicity of the two states involved in the radiative transition (typically
an electronically
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excited state and the ground state) have identical spin multiplicities. A
lumophore is an
emissive compound in which one of the two states involved in the radiative
transition
.(typically the electronically excited state) derives from substantial mixing
of two or more
orbital configurations having different spin multiplicities [see for example,
Lakowicz, J. R.
Principles of Fluorescence Spectroscopy (Plenum Press, New York, 1983); Turro,
N. J.
Modern Molecular Photochemistry (The Benjamin/Cummings Publishing Co., Inc.,
Menlo
Park, 1978)]. A phosphore according to the invention is an emissive compound
in which the
spin multiplicity of the two states involved in the radiative transition
(typically an
electronically excited state and the ground state) differ in their respective
spin multiplicities.
A laser dye according to the invention is any organic, inorganic, or
coordination compound
that has been established previously to lase. Representative laser dyes can be
found in Birge,
R. R.; Duarte, F. J. Kodak Optical Products, Kodak Publication JJ-169B (Kodak
Laboratory
Chemicals; Rochester, NY (1990). Representative laser dyes include:
p-terphenyl Sulforhodamine B
p-quaterphenyl Rhodamine 101
carbostyryl 124 Cresy Violet perchlorate
popop DODC Iodide
Coumarin 120 Sulforhodamine 101
Coumarin 2 Oxazine 4~ perchlorate
Coumarin 339 DCM
Coumarin 1 Oxazine 170 perchlorate
Coumarin 138 Nile Blue A Perchlorate
Coumarin 106 Oxatine 1 Perchlorate
Coumarin 102 Pyridine 1
Coumarin 314T Styryl 7
Coumarin 338 HIDC Iodide
Coumarin 151 DTPC Iodide
Coumarin 4 Cryptocyanine
Coumarin 314 DOTC Iodide
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Coumarin 30 HITC Iodide
Coumarin 500 HITC Perchlorate
Coumarin 307 DTTC Iodide
Coumarin 334 DTTC Perchlorate
Coumarin 7 IR-144
Coumarin 343 HDITC Perchlorate
Coumarin 337 IR-140
Coumarin 6 IR-132
Coumarin 152 IR-125
Coumarin 153 Boron-dipyrromethene
HPTS Flourescein
Rhodamine 110 2, 7-dichlorofluorescein
Rhodamine 6G Rhodamin 19 Perchlorate
Rhodamine B
In preferred embodiments, the electronic structure of the component moieties
in
compounds of the invention are similar. The respective one-electron oxidation
and reduction
potentials thereof preferably differ by less than 250 mV. The energies of the
respective
lowest energy electronic transitions preferably differ by less than 2500 cm'.
It has been found in accordance with the present invention that a wide variety
novel
highly conjugated porphyrin-based chromophore systems of the invention have
unusual
electooptic properties, and can function as collective oscillators. The
formation of a
collective oscillator and cooperative emission requires coupling of the
transition dipoles of
monomeric pigments. The compounds in the preferred embodiment of the invention
are a
class of multichromophoric systems that display extremely strong pigment-
pigment electronic
coupling; these assemblies feature ethyne and butadiyne moieties that directly
link the carbon
frameworks of their constituent porphyrin building blocks (FIG. 1). These
ethyne- and
butadiyne-bridged porphyrin arrays exhibit a number of surprising and
unexpected
optoelectronic characteristics, and are remarkable in that their optical
absorption profiles,
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emission wavelengths, redox properties, as well as spin distribution and
orientation in their
photoactivated triplet states, are regulated extensively by the mode of
porphyrin-to-porphyrin
linkage topology. The ability to modulate comprehensively such a broad range
of
photophysical properties stems from flexible synthetic methodology that
permits the extent of
ground- and excited-state electronic coupling between pigments in these
systems to be varied
over a wide range. Notably, because the magnitude of pigment-pigment
electronic
interactions in these supramolecular assemblies is large relative to the
vibronic modes that
typically broaden electronic transitions irrespective of the nature of
chromophore-
chromophore connectivity, molecular structure regulates intimately the nature
of pigment
transition dipolar interactions and the corresponding photophysics of their
respective
electronically excited singlet states.
In preferred embodiments, the compounds of the invention are synthetic
multichromophoric systems that exhibit one or more of the following optical
properties: (i)
low energy emission excited states in which the transition dipoles of the
constituent pigment
building blocks are correlated in defined phase relationships, (ii) excited
state polarization
over long timescales, (iii) emission quantum yields that have an unusual
dependence upon
supramolecular structure and emission wavelength, (iv) the hallmarks of
collective oscillator
behavior in their respective electronically-excited states, and (v) extreme
superradiance, the
magnitude of which exceeds the maximal value predicted classically (eq 1 ).
Integrated
emission oscillator strengths that are large with respect to that manifest by
the benchmark
monomeric chromophore.
In another aspect of the invention, the multichromophoric systems are
generated by
the process of providing a conjugated compound comprising at least two
covalently bound
moieties and exposing the conjugated compound to an energy source for a time
and under
conditions effective to cause the compound to emit light. The light emitted is
preferably in
the range of 650-2000 nm. The moieties used are, for example, porphyrins, and
they may be
bound by at least one carbon-carbon double bond, carbon-carbon triple bond, or
a
combination thereof. The bond can be, for example, ethynyl, ethenyl, allenyl,
or butadiynyl.
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In another aspect of the invention, the moities may, for example, be bound by
a combination
of those units, or at least one imine, phenylene, or thiophene group.
Time-Resolved Fluorescence Spectroscopy
In the present invention, the isotropic and anisotropic dynamics of the lowest
energy
singlet excited (S 1 ) states of benchmark ethyne-elaborated
(porphinato)zinc(II) monomers (5-
ethynyl-10,20-diphenylporphinato)zinc(II) (Compound 1), (5,15-diethynyl-10,20-
diphenylporphinato)zinc(II) (Compound 2), and (2-ethynyl-5,10,15,20-
tetraphenylporphinato)zinc(II) (3) as well as those of conjugated
(porphinato)zinc(II) arrays
(Compounds 4-12) (FIG. 1) were characterized employing the time-correlated
single-photon
counting (TCSPC) spectroscopic technique.
The fluorescence anisotropy (r(t)) measured at time t following optical
excitation is
obtained from the parallel (I,i ) and perpendicular (I1) transient signals
using the
following expression:
I ~(t)-I1(t)
r(t) I 1(t) + 2I1(t) (2)
The magnitude of the initial anisotropy, r(p~ , depends on the respective
degeneracies and
polarizations of the absorptive and emissive states. The value of r(p) in a
dilute solution (eq
3) is a product of the angular displacement (a) of the absorption and emission
dipoles and the
loss of anisotropy due to photoselection (2/5).
_2 3 cost a -1
ro> - 5 2
In the absence of coherence effects, initial fluorescence anisotropies for
chromophore systems
based on (porphinato)metal species will fall into four limiting cases: (i) if
the excited-state
degeneracy is not broken, the initial excited state population will randomize
between
orthogonal and energetically equivalent x-and y-polarized S 1 states, giving
rise to a r~o~ value
of 0.1; (ii) when excited-state degeneracy is removed and the absorption and
emission dipoles
are parallel (a= 0), r~o~ will equal 0.4; (iii) when excited-state is singly
degenerate and the
absorption and emission dipoles are orthogonal (a= 90°), a r~o~ value
of -0.2 will be observed;
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and (iv) if overlapping (multiple) states of different polarizations and
degeneracies are either
pumped or probed, r~o~ values intermediate between the -0.2 and 0.4 extremes
will be
manifest. It is important to note that, for the present invention, the actual
measured value of
r~o~ depends intimately upon the experimental timescale; for example, if the
interrogated
absorption and emission dipoles are parallel, but an experimentally determined
value of r~o~
less than 0.4 is manifest, it generally indicates the existence of relaxation
processes that occur
on time scales shorter than the time resolution of the experiment. Such
processes can involve
nuclear dynamics (e.g., rotational or librational motion) of the molecule, or
electronic
(vibronic) relaxation pathways. Hence, in the present invention the degree of
energetic
splitting between orthogonal excited states, as well as chromophore size and
shape, will
determine the timescales over which the fluorescence anisotropy decays to zero
(r(t) = 0) and
whether or not the experimental time domain is adequate to measure initial
anisotropy values
at the 0.4 and -0.2 extrema.
SI-excited state lifetime and time-resolved fluorescence anisotropy data for
the
present invention are summarized in FIG. 4 for compounds 1-12; typical
isotropic (magic
angle) and anisotropic fluorescence decay profiles for these species are
presented in FIG. 2.
In these experiments, samples were excited on the low energy side of their
respective lowest
energy Q absorption bands; fluorescence decays were probed at wavelengths to
the red of the
emission ~,max. Monoexponential decay of the isotropic fluorescence was
observed (FIG.
4); notably, all of these species of the present invention possess similar
(ns) fluorescence
lifetimes (iF). In contrast, the anisotropic fluorescence dynamics vary
extensively in
compounds 1-12 of the present invention. 5,10,15,20-
Tetraphenylporphinato)zinc(II)
(TPPZn), a porphyrinic photophysical benchmark, possesses a doubly degenerate
S 1 excited
state and displays an initial anisotropy (r~o~ = 0.1; t = 20 ps) following
electronic excitation on
the red edge of the lowest energy Q transition. The measured values of the
initial anisotropy
(r~o~ = 0.2; t = 20 ps) for compounds 1, 2, and 3 of the present invention
show that expansion
of porphyrin conjugation via meso-ethynyl moieties introduces an electronic
perturbation
sufficient to cause a splitting of the x- and y-polarized transitions.
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Compounds 4-12 of the present invention express fluorescence anisotropies
measured
20 ps after excitation that range from 0.1 to 0.4, indicating that
chromophoric excited states
can be prepared that range from doubly degenerate and nonpolarized (r~o~ =
0.1), to singly
degenerate and highly polarized (r~o~ = 0.4). The nature of the porphyrin-to-
porphyrin linkage
topology is clearly important in establishing the magnitude of the initial
anisotropy. Note
that (3-to-(3 bridged chromophores display r0 values of ~0.1 (compounds 4, 7,
and 10), while
only meso-to-meso bridged (porphinato)zinc(II) chromophores (compounds 6, 9,
11, and 12)
exhibit values of 0.4. In addition to the topologically dependent magnitude of
pigment-
pigment electronic coupling, the extent of conformational mobility about the
conjugated
bridge likely plays a role in determining the magnitude of r~o~ in meso-to-(3
bridged pigments
(compounds 5 and 8).
Time-resolved experimental data show that the initial anisotropies for
compounds 4-
12 of the present invention decay typically via single exponential processes;
these results
indicate that the fluorescence anisotropy at time t after excitation is
determined by the
magnitude of the rotational diffusional time constant (ir), [r(t) = roes-
~~T~~]. These data evidence
that fast electronic dephasing processes are absent, and that the phase
relationship of the
individual pigment dipoles remain correlated throughout the entire lifetime of
the S,-excited
state in compounds 4-12; this is seen most dramatically in meso-to-meso ethyne-
and
butadiyne-bridged compounds 6, 9, 11, and 12, which manifest emissive, singly
degenerate S,
states polarized exclusively along their respective highly conjugated axes.
The fact that, in the preferred embodiment, ethyne- and butadiyne-bridged
porphyrin
arrays 4-12 display fluorescence lifetimes (0.9 5 iF <_ 1.7 ns) similar in
magnitude to that
exhibited by their respective conjugated, monomeric building blocks 1-3 (1.5
<_ iF <_ 2.2 ns),
underscores the unusually long timescales over which excited state
polarization can be
maintained. Note that the emission maxima of compounds 4-12 span a 4,000 cm'
energy
domain (621 - 836 nm; FIG. 1), indicating that both fluorescence wavelength
and excited-
state anisotropy can be highly modulated in these systems without significant
diminution of
~F~
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Superradiant Emission
FIG. 5 chronicles the Stokes shifts, B- and Q-state transition dipole moments,
and
fluorescence quantum yields (QYs) for compounds 1-12. Note that emission QYs
of ethyne-
elaborated monomeric porphyrin compounds 1-3 exceed that measured for TPPZn
and (5,15-
diphenylporphinato)zinc(II) (DPPZn) benchmarks. Congruently, QYs determined
for bis-
and tris[(porphinato)zinc(II)] compounds 4-12 are larger than that measured
for the
monomers 1-3; note also that for both bis-(compounds 4-9) and
tris[(porphinato)zinc(II)]
(compounds 10-12) species, the absolute magnitudes of the QYs vary with
linkage topology
and the length of the cylindrically ~-symmetric bridge that connects the
aromatic
macrocycles. When analyzed in context of the dynamical data presented in FIG.
4, the
results summarized in FIG. 5 lead to a number of startling conclusions.
It has been noted that when the excited-state energy is modulated in a series
of
compounds based on a single emissive chromophore, the observed radiationless
decay rate
constant (kin.) for a specific pigment should follow a predictable dependence
upon the
respective degree of vibrational overlap between the relevant ground and
excited states. This
quantum effect is commonly referred to as the energy gap law; FIG. 3A,
highlights its
dependence upon extent of initial and final state energy separation, and the
magnitude of
equilibrium nuclear displacement (0Q) between these electronic states. As
shown in FIG.
3A potential energy diagrams 1 and 2, decreasing the So S, energy gap leads to
enhanced
vibrational wavefunction overlap, which effects a corresponding increase in
knr. Because i~
is equal to the inverse sum of the radiative (k,.) and nonradiative rate
constants (i,; _ ~kr + k~~~' ~ excited state lifetimes diminish
correspondingly with decreasing
emission energies. This simple prediction has now been verified in a number of
pigment
systems.
When a significant deviation from the expected linear dependence of ln(knr)
upon
emission energy is observed within a series of related chromophores, it
typically indicates
that equilibrium ground- and excited-state nuclear displacements are not
uniform within these
pigments. Relevant to this study, it is important to point out that
progressive expansion of
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chromophore conjugation has been established as a facile means to introduce
such electronic
structural perturbations. This is shown in FIG. 3A potential energy diagrams 1
and 3; note
as OQ decreases at a constant So-S, energy separation, vibrational overlap
decreases thus
diminishing the magnitude of km.. This effect is well documented in classic
work by Meyer ,
which shows that augmentation of ~ electronic delocalization in ruthenium
polypyridyl
complexes results in substantially diminished k"' values and enhanced emission
lifetimes
relative to the ruthenium tris(bipyridyl) archetype; such an approach provides
a viable
strategy to engineer long-lived pigment excited states that possess emission
energies that are
reduced relative to the parent chromophore.
It is crucial to note, however, that the fabrication of red-emitting
chromophores
possessing long excited-state lifetimes via such an energy-gap-law-based a
strategy does not
come without a price. Because the size of the radiative rate constant lc'
decreases
substantially within a given class of isolated chromophores as the optical
band gap narrows
(eq 1 ), the magnitude of the emission quantum yield (QY; QY = k' ) falls
(k' + kn' )
dramatically. Engineering even modest shifts of emission energy (on the order
of 2000 cm
~) through chromophore conjugation expansion, has been shown to effect greater
than ten-fold
reductions in the observed emission QY with respect to that of the original
pigment complex.
Taken in context of this discussion of the energy gap law, compounds 4-12 of
the
present invention are spectacular in that they exhibit both long fluorescence
lifetimes and
emission quantum yields that exceed significantly that of their constituent
(porphinato)zinc(II) building blocks; importantly, the fluorescence QYs for
compounds 4-12
are substantially augmented relative to simple (porphinato)zinc(II) complexes,
despite the fact
that the 7~e,n maxima for these species reside 700 to 4600 cm' lower in energy
than that for
the TPPZn reference chromophore (FIGS. 4-6). Because the radiative transition
probability
is proportional to the cube of the emission energy (eq 1), in order for
compounds 4-12 of the
present invention to feature simultaneously substantial fluorescence lifetimes
and emission
quantum yields relative to their monomeric (porphinato)zinc(II) benchmarks,
these
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multichromophoric systems must be behaving as collective oscillators((~,~4-~Z
» (~~TPPZn)
(eq 1 ).
The extent to which a pigment aggregate is superradiant is generally expressed
in
terms of a superradiance enhancement factor (emitting dipole strength) in
which the
experimentally determined <~.1>ass~egate value is reference against <~>
measured for an
appropriate monomeric pigment benchmark. The superradiance enhancement factor
is thus a
direct observable that is often taken as a classical measure of the exciton
diffusion length.
Emitting dipole strengths (EDSs) and radiative lifetimes (i~ad) for compounds
1-12 are
listed in FIG. 6. While these data show that, in the present invention, bis-
and tris(pigment)
arrays 4-12 all manifest dramatic superradiance enhancement factors, the
magnitudes of the
EDSs determined for oligo[(porphinato)zinc(II)] systems of the present
invention featuring
meso-to-meso or meso-to-~3linkage topologies (compounds 5, 6, 8, 9,11, and 12)
are
particularly striking: they greatly exceed the expected maximal values (i.e.,
2 and 3) predicted
for ensembles composed of two and three respective monomeric pigment units (eq
1 ).
EDS values of this magnitude for similarly sized conjugated oligomers are
without
precedent. Likewise, superradiant conjugated polymers fabricated to date have
exploited
monomer units with transition dipole moments considerably smaller than that
manifest by
porphyryl moieties. Given the lack of appropriate photophysical benchmarks
among
superradiant conjugated organic materials, it is useful to compare these data
to those obtained
for the superradiant biological light harvesting proteins, which feature
strongly-coupled
chromophore ensembles composed of similar pigment monomeric units
(bacteriochlorophylls
and chlorophylls). Analogous data obtained for the biological benchmarks are
shown for
comparison in FIGS. 4-6. Using the EDS of the bacteriochlorophyll a (Bchl a)
monomer as
a chromophoric reference, and analyzing appropriate photophysical data
obtained for the
B820 subunit of the LH-2 protein of Rhodospirillum rubrum and the intact light
harvesting
complexes LH-1 and LH-2 of Rhodobacter sphaeroides in terms of the Einstein
relation (eq
1 ), van Grondelle has shown that the superradiance enhancement factors for
these biological
pigment-protein complexes are respectively 1.3, 2.8, and 3.8. These results
implied that the
exciton diffusion lengths in the long-wavelength absorbing pigment assemblies
of B820, LH-
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1, and LH-2 corresponded to distances defined by these respective numbers of
Bchl a units;
because the strongly coupled chromophore arrays of B820, LH-1, and LH-2
possess
respectively 2, 16, and 32 pigments, these experiments suggested that while
the extent of
excited-state delocalization is significant in these LHCs, it is not global in
nature.
Clearly, the EDSs determined ethyne- and butadiyne-bridged
(porphinato)zinc(II)
arrays that feature meso-to-meso or meso-to-~ linkage motifs must arise from
factors
supplemental to the collective, in-phase oscillation of the individual pigment
dipoles in these
conjugated chromophore systems. These EDSs can be rationalized considering the
established triplet photophysics of these species. In contrast to the singlet
excited states of
compounds 6, 8, 9, 11, and 12, which evince substantial delocalization of
electron density,
photoexcited EPR spectroscopic studies establish conclusively that the T,-
excited-state
electron density distributions in compounds 4-12 of the present invention are
all highly
localized. Importantly, these experiments show that the spatial extent of T,-
state
wavefunction in these species in no case exceeds the dimensions defined by a
single
(porphinato)zinc(II) unit and its pendant, cylindrically ~-symmetric (ethyne
or butadiyne)
substituents. The genesis of this T, wavefunction localization in compounds 4-
12 may derive
from large lattice relaxations, which are known to diminish the spatial extent
of triplet
electronic states relative to excited S~ states in oligophenylene ethynylenes,
or from
fundamental electronic differences between the singlet and triplet excitation
manifolds that
can be rationalized within the context of the point-dipole approximation of
the general
exciton model.
Because the exciton resonance scales with the square of the transition moment,
it is
likely that high oscillator strength absorbers (compounds 4-12) possess
unusually large
Franck-Condon barriers to S,-T, intersystem crossing. Moreover, as S, excite-
state electronic
delocalization increases in this series (~,e", increases), these Franck-Condon
barriers would be
expected to increase progressively as well FIG. 3B, since similar, highly
localized T, states
are manifest for a given porphyrin-to-porphyrin linkage topology regardless of
the size of the
pigment array. Because iF = (k~ + kn~ )-', and the magnitude of the
nonradiative decay rate
28
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WO 02/104072 PCT/US02/05584
constant k"~ corresponds to the sum of all kinetic processes that non-
emissively quench the S,-
excited state (k"r k,c + k,sc, where k,sc = S,-T, intersystem crossing rate
constant and k,c
represents the overall rate constant for the S,-So non radiative internal
conversion process), as
k,sc ~ 0, the magnitude of the fluorescence lifetime correspondingly increases
FIG. 3B. As
noted above, the energy gap law predicts that decreased So S, energy
separations will lead to
increased values of k,c within a given class of chromophores; while this
undoubtedly plays a
role in the S, photophysics for compounds 4-12, at least over the emission
energies spanned
by these species, augmentation of the magnitude of k,c is apparently more than
compensated
by the corresponding diminution of k,sc with increasing ~, em . This effect
causes the
magnitude of the fluorescence lifetime to remain relatively constant
throughout compounds
1-12, and is a primary determinant for the unusually large fluorescence QYs
observed for the
red-emitting chromophores in this series. Thus, in addition to in-phase
oscillation of strongly
coupled pigment transition dipoles, concomitant reduction of k,sc with
increased S,-state
electronic delocalization for these species plays a key role in establishing
the extreme
superradiant behavior highlighted in FIG. 6.
This work shows that excited-state deactivation pathways that dominate the
photophysics of monomeric pigments need not necessarily control the excited-
state dynamics
of their corresponding strongly-coupled chromophore assemblies; hence the
supermolecular
multipigment systems of the present invention that exist as distinct
photophysical entities can
be constructed from simple chromophoric building blocks. These ethyne- and
butadiyne-
bridged (porphinato)zinc(II) assemblies show the essential characteristics of
the pigment
assemblies of the biological light harvesting proteins: substantial pigment-
pigment coupling,
high excited-state polarization, and coupled oscillator photophysics. When
such conjugated
assemblies are engineered to possess singly degenerate excited states, high
and low frequency
vibrational modes of the chromophore and solvent do not significantly impact
excited-state
electronic dephasing, and the polarized, dipole-dipole correlated nature of
these singlet
excited states is maintained over long, ns timescales.
Analysis of the fluorescence intrinsic decay rate and quantum yield data show
that in
the present invention the ethyne- and butadiyne-bridged multiporphyrin species
that manifest
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WO 02/104072 PCT/US02/05584
high excited-state anisotropies display extreme superradiance enhancement
factors: such
photophysics derive from the fact that these conjugated pigment arrays behave
as collective
oscillators, and feature large Frank-Condon barriers for intersystem crossing
between their
respective S, and T, states. These results indicate that substantial emitting
dipole strengths
can in fact be realized for low energy fluorescing materials, and that classic
energy gap law
considerations that place important restrictions upon the elaboration of
isolated pigments that
manifest high quantum yield, low energy fluorescence, do not preclude the
design of
supermolecular systems that manifest such photophysics.
Finally, this work suggests that the combination of monomer units having large
absorption oscillator strengths, with monomer-to-monomer linkage motifs that
assure strong
coupling, dipole-dipole alignment, and large values of the excited-state
anisotropy, may
constitute a general strategy for the fabrication of electrooptic materials
that exhibit extreme
superradiance. Because low energy optical band gaps, high anisotropy singlet
excited-states,
and extreme superradiance can be engineered in parallel, the design concepts
articulated
herein bear relevance to the fabrication of photonic materials, and device
applications where
pigment organization, divergent cross sections for singlet and triplet exciton
formation from
injected charge carriers, and large optical gain, are held at a premium.
Additional objects, advantages, and novel features of this invention will
become
apparent to those skilled in the art upon examination of the following
examples thereof,
which are not intended to be limiting. Additional synthetic techniques for
compounds of the
invention are disclosed in: (1) Highly-Conjugated, Acetylenyl-Bridged
Porphyrins: New
Models for Light-Harvesting Antenna Systems, V. S.-Y. Lin, S. G. DiMagno, and
M. J.
Therien, Science (Washington, D. C.) 1994, 264, 1105-1111; (2) The Role of
Porphyrin-to-
Porphyrin Linkage Topology in the Extensive Modulation of the Absorptive and
Emissive
Properties of a Series of Ethynyl- and Butadiynyl-Bridged Bis- and
Tris(porphinato)zinc
Chromophores, V. S.-Y. Lin and M. J. Therien, Chem. Eur. J. 1995, l, 645-651;
(3) Singlet
and Triplet Excited States of Emissive, Conjugated Bis(porphyrin) Compounds
Probed by
Optical and EPR Spectroscopic Methods, R. Shediac, M. H. B. Gray, H. T. Uyeda,
R. C.
CA 02439060 2003-08-21
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Johnson, J. T. Hupp, P. J. Angiolillo, and M. J. Therien, J. Am. Chem. Soc.
2000,122, 7017-
7033.
EXAMPLE 1
5,15-DIPHENYLPORPHYRIN
A flame-dried 1000 ml flask equipped with a magnetic stirring bar was charged
with
2,2-dipyrrylmethane (458 mg, 3.1 mmol), benzaldehyde (315 ~ 1, 3.1 mmol), and
600 ml of
freshly distilled (CaHz) methylene chloride. The solution was degassed with a
stream of dry
nitrogen for 10 minutes. Trifluoroacetic acid (150 p l, 1.95 mmol) was added
via syringe, the
flask was shielded from light with aluminum foil, and the solution was stirred
for two hours
at room temperature. The reaction was quenched by the addition of 2,3-dichloro-
5,6-dicyano-
1,4-benzoquinone (DDQ, 900 mg, 3.96 mmol) and the reaction was stirred for an
additional
30 minutes. The reaction mixture was neutralized with 3 ml of triethylamine
and poured
directly onto a silica gel column (20 x 2 cm) packed in hexane. The product
was eluted in 700
ml of solvent. The solvent was evaporated, leaving purple crystals (518 mg.,
1.12 mmol,
72.2%). This product was sufficiently pure for further reactions. Vis(CHC13):
421 (5.55), 489
(3.63), 521 (4.20), 556 (4.04), 601 (3.71), 658 (3.73).
EXAMPLE 2
5,15-DIBROMO-10,20-DIPHENYLPORPHYRIN
5,15-Diphenylporphyrin (518 mg, 1.12 mmol) was dissolved in 250 ml of
chloroform
and cooled to Oo C. Pyridine (0.5 ml) was added to act as an acid scavenger. N-
Bromosuccinimide (400 mg, 2.2 mmol) was added directly to the flask and the
mixture was
followed by TLC (50% CHzCl2/hexanes eluant). After 10 minutes the reaction
reached
completion and was quenched with 20 ml of acetone. The solvents were
evaporated and the
product was washed with several portions of methanol and pumped dry to yield
587 mg (0.94
mmol, 85%) of reddish-purple solid. The compound was sufficiently pure to use
in the next
reaction. Vis(CHCl3): 421 (5.55), 489 (3.63), 521 (4.20), 556 (4.04), 601
(3.71), 658 (3.73).
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EXAMPLE 3
5,15-DIBROMO-10,20-DIPHENYLPORPHYRINATO ZINC
5,15-Dibromo-10,20-diphenylporphyrin (587 mg, 0.94 mmol) was suspended in 30
ml
DMF containing 500 mg ZnCl2. The mixture was heated at reflux for 2 hours and
poured into
distilled water. The precipitated purple solid was filtered through a fine
fritted disk and
washed with water, methanol, and acetone and dried in vacuo to yield 610 mg
(0.89 mmol,
95%) of reddish purple solid. The compound was recrystallized from THF/heptane
to yield
large purple crystals of the title compound (564 mg, 0.82 mmol, 88%).
Vis(THF): 428 (5.50),
526 (3.53), 541 (3.66), 564 (4.17), 606 (3.95).
EXAMPLE 4
MESO-SUBSTITUTED PORPHYRINS
General Procedure
In each of the following examples, 5,15-Dibromo-10,20-diphenylporphyrinato
zinc
(0.1 mmol), and Pd(PPh3)4 (0.0025 mmol) were dissolved in 35 ml of distilled,
degassed
THF in a sealed storage tube with the 1 mmol of the indicated organometallic
reagent and
warmed at 60o C. for 48 hours. The reaction was monitored by TLC on withdrawn
aliquots.
The mixture was quenched with water, extracted with chloroform, dried over
CaCl2,
evaporated and purified by column chromatography.
A. 5,15-biphenyl-10,20-dimethylporphyrinato zinc
The organometallic reagent was methyl zinc chloride prepared from methyl
lithium
and anhydrous zinc chloride in THF. .
The crude solid was dissolved in THF/heptane, poured onto 10 g silica gel and
evaporated to dryness. This silica gel was loaded onto a column packed in 50%
CHZC12/hexane. A single band was eluted (50% CHZCl2/hexane) to yield pure 5,15-
diphenyl-
10,20-dimethylporphyrinato zinc (48 mg, 88%). An analytical sample was
recrystallized from
THF/heptane by slow evaporation under N2. ' H NMR (S00 MHz, 3:1 CDC13, D8-THF)
epsilon 9.34 (d, 4H, J = 4.6); 8.71 (d, 4H, J = 4.6); 8.02 (dd, 4H, J1 = 7.5,
J2 = 1.4); 7.57 (m,
6H); 4.51 (s, 6H). '3 C NMR (125 MHz, 3:1 CDC13, Da-THF) epsilon 150.07 (0),
148.88 (0),
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143.34 (0), 134.18 (1), 131.42(1), 128.09(1), 126.73(1), 125.88(1), 119.29(0),
113.74(0),
20.81(3). Vis (THF) 424 (5.58), 522 (3.40), 559 (4.12); 605 (3.88).
B. 5,15-biphenyl-10,20-divinylporphyrinato zinc
The organometallic reagent was tri-n-butylvinyl tin.
The crude product was absorbed on silica and loaded onto a column packed in
hexane.
Elution was carried out with CHZC12(0-50%)/hexane. A small quantity of purple
material led
the main fraction. The main band was evaporated to yield pure 5,1 S-diphenyl-
10,20-
divinylporphyrinato zinc (53 mg, 91 %). An analytical sample was
recrystallized from
chloroform. ' H NMR (500 MHz, CDC13) epsilon 9.52 (d, 4H, J = 4.7); 9.24(dd,
2H, J1 =
17.3, J2 = 9.1); 8.92 (d, 4H, J = 4.7); 8.19 (dd, 4H, J1 = 6.8, J2 = 2.0);
7.75 (m, 6H); 6.48 (dd,
2H, J1 = 11.0, J2 = 1.9); 6.05 (dd, 2H, J1 = 17.3, J2 = 2.0). '3 C NMR (125
MHz, CDC13)
epsilon 163.40(1), 149.90(0), 149.21( 0), 142.83(0), 137.97(0), 134.40(1),
132.10(1),
130.39(1), 127.50(1), 126.73(2), 126.57(1), 121.05(0).
C. 5,15-Bis(2,5-dimethoxyphenyl)-10,20-diphenylporphyrinato zinc
The organometallic reagent was 2,5-dimethoxyphenyl lithium, prepared from 1,4-
dimethoxybenzene and t-butyl lithium in ether at - 78° C. The
organolithium reagent was
added to a solution of ZnClz in THF to yield the organozinc chloride reagent.
This reagent
was used immediately.
At the completion of the reaction two highly fluorescent spots were visible by
TLC.
The crude product was chromatographed on silica using CHCI, as eluant. The
first band off
the column proved to be the CZh isomer of 5,15-bis(2,5-dimethoxyphenyl)-10,20-
diphenylporphyrinato zinc. This band was evaporated leaving 33 mg (42%) of
pure product.
An analytical sample was recrystallized from chloroform. ' H NMR (500
MHz,CDCI~)
epsilon 8.91 (s, 8H); 8.22 (d, 4H, J = 6.5); 7.75 (m, 6H); 7.59 (d, 2H, J =
2.2); 7.26 (broad s,
4H); 3.86 (s, H); 3.54 (s, 6H).'3 C NMR (125 MHz, CDCI~) epsilon 154.10(0),
152.30(0),
150.13(0), 143.00(0), 134.10(1), 132.62(0), 132.00(1), 131.44(1), 127.35(1),
126.44(1 ),
121.34(1), 120.69(0), 110.59(0), 114.76(1), 112.31(1), 56.70(3), 55.95(3). Vis-
424 (5.64),
551 (4.34), 584 (3.43).
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The Czv isomer followed the CZh isomer off the column. The solvent was
evaporated leaving 30 mg (32%) of pores, 15-bis(2,5-dimethoxyphenyl)-10,20-
diphenylporphyrinato zinc. This compound is much more soluble in chloroform
than the CZh
isomer. The assignment of stereochemistry was made from the NMR data. ' H NMR
(500
MHz,CDCl3) epsilon 8.90 (s, 8H); 8.21 (d, 2H, J = 7.9); 8.19 (d, 2H, J = 6.5);
7.73 (m, 6H);
7.58 (s, 2H); 7.24 (broad s, 4H); 3.84 (s, 6H); 3.53 (s, 6H). '3 C NMR (125
MHz CDCI;)
epsilon 154.14 (0); 152.31 (0), 150.15 (0), 142.94(0), 134.40(1), 132.66(0),
132.02(1),
131.48(1), 127.37(1), 126.46( 1), 126.44(1), 121.30(1), 120.72(0), 116.69(0),
114.73(1),
112.28(1), 56.75(3), 55.92(3).
D. 5,15-Bis[(4-methyl)-4'-methyl-2,2'-dipyridyl)]-10,20-diphenylporphyrinato
zinc
The organometallic reagent was tri-n-butyl[(4-methyl)-4'-methyl-2,2'-
dipyridyl)]tin,
prepared by lithiating 4,4'-dimethyl-2,2'-dipyridyl with one equivalent of
lithium
diisopropylamide in THF at - 78° C. and warming the reaction mixture to
room temperature.
The organolithium reagent was treated with 1.1 equivalent of tributyltin
chloride. The
resulting organotin reagent was used without further purification.
Chromatography of the crude reaction mixture was carried out on silica with a
mixture of CHzCl2, isopropanol, and triethylamine. The porphyrin was eluted in
one broad
band. The product obtained from this procedure (68% yield) was contaminated
with a small
amount (0.2 eq per eq of porphyrin) of triphenylphosphine. 'H NMR (500 MHz,
CDCl3)
epsilon 9.37 (d, 4H, J = 4.7); 8.87 (d, 4H, J = 4.7); 8.52 (s, 2H); 8.29 (d,
2H, J = 5.1 ); 8.20 (d,
2H, J = 5.2); 8.10 (m, 6H); 7.71 (m, 6H); 7.01 (d, 2H, J = 5.0); 6.88 (d, 2H,
J = 4.2); 6.46 (s,
4H); 2.32 (s, 6H).
E. 5,15-Bis(trimethylsilylethynyl)-10,20-diphenylporphyrinato zinc
The organometallic reagent was trimethylsilyl ethynyl zinc chloride prepared
from
trimethylsilylethynyl lithium and anhydrous zinc chloride in THF.
After 48 hours the reaction was bright green. The crude solid was absorbed on
silica
gel, loaded onto a column packed in hexane, and chromatographed with 20%-30%
CHZCl2/hexane. Clean separation of the product from the small quantities of
deprotected
products were obtained by this method. The solvents were evaporated and the
purple solid
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WO 02/104072 PCT/US02/05584
was washed twice with hexane and dried in vacuo. ' H NMR (500 MHz, CDC13)
epsilon 9.68
(d, 4H, J = 4.6); 8.89 (d, 4H, J = 4.6); 8.15 (dd, H, J1 = 7.9, J2 = 1.7);
7.75 (m, 6H); 0.58 (s,
18H). " C NMR (125 MHz, CDC13) epsilon 152.22, 150.26, 142.10, 134.39, 132.77,
131.29,
27.69, 126,67, 115.08, 107.34, 102.00, 0.32.
EXAMPLE 5
PYRROLE-SUBSTITUTED PORPHYRINS
General Procedure
2-Bromo-5,10,15,20-tetraphenylporphyrinato zinc (0.1 retool) and palladium
1,1'-bis
(diphenylphosphino) ferrocene) dichloride (Pd(dppf)C12, 7 mg) were combined
with 1.0
mmol of the organometal lic reagent indicated below in 35 ml dry, degassed
THF. The
solution was allowed to stand for 12 hours, the solvent evaporated, and the
compound
purified by flash chromatography.
A. 2-Vinyl-5,10,15,20-tetraphenyl porphyrinato zinc
The organometalic reagent was tributylvinyl tin.
The crude reaction mixture was chromatographed on silica and eluted with 50%
CHZC12/hexane. ' H NMR (250 MHz, CDC13) epsilon 8.97 (s, 1 H); 8.90 (m, 4H);
8.87 (d, 1 H,
J = 4.7); 8.79 (d, 1H, J = 4.7); 8.20 (m, 6H); 8.06 (d, 2H, J = 6.6); 7.74 (m,
12H); 6.39 (dd,
1 H, J 1 = 17.0, J2 = 9.1 ); 5.83 (dd, 1 H, J 1 = 17.1, J2 = 2.0); 5.01 (dd, 1
H, J 1 = 10.7, J2 = 2.0).
Vis (CHC13) 426 (5.53), 517 (3.68); 555 (4.22), 595 (3.68).
B. 2-(2,5-dimethoxyphenyl)-5,10,15,20-tetraphenyl porphyrinato zinc
The organometallic reagent was 2,5-dimethoxyphenyl zinc chloride, prepared
from
the corresponding lithium reagent and anhydrous zinc chloride in THF/diethyl
ether.
Flash chromatograph of the crude reaction mixture was carried out with
chloroform.
The title compound was isolated in 78% yield. ' H NMR (500 MHz, CDC13) epsilon
= 8.94
(d, 1 H, J = 4.7); 8.93 (s,2H); 8.92 (d, 1 H, J = 4.8); 8.85 (s, 1 H); 8.84
(d, 1 H, J = 4.7); 8.70 (d,
1H, J = 4.7); 8.23 (m, 6H); 7.98 (d, 1H, J = 7.0); 7.70 (m, 1 OH); 7.25
(quintet, 2H, J = 7.4);
7.15 (t, 1 H, J = 7.0); 6.92 (d, 2H, J = 3 .1 ); 6.54 (dd, 1 H, J 1 = 9.0, J2
= 3.2); 6.40 (d, 1 H, J =
9.1); 3.68 (s, 3H); 3.42 (s, 3H). " C NMR (125 MHz, CDCI,) epsilon =
152.59(0), 151.33(0),
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WO 02/104072 PCT/US02/05584
150.46(0), 150.31(0), 150.27(0), 150.15(0), 150.12(0), 150.03(0), 148.30(0),
147.16(0),
143.32(0), 142.97(0), 142.86,140.71(0), 135.63(1), 135.20(1), 134.45(1),
134.13(1),
132.52(1), 132.02(1), 131.91(1), 131.82(1), 131.32(1), 129.27(0), 127.44(1),
127.38(1),
127.18(1), 126.53(1), 126.50(1), 124.91(1), 121.70(1), 122.36(0), 121.30(0),
120.91(0),
120.54(0), 113.15(1), 113.03(1), 110.35(1), 55.98(3), 54.87(3). Vis (CHC13)
421.40(5.60),
513.2 (3.45), 549.75 (4.28), 587.15 (3.45).
C. 2-(Trimethylsilylethynyl)-5,10,15,20-tetraphenyl porphyrinato zinc
The organometallic reagent, trimethylsilylacetylide zinc chloride, was
prepared from
. the corresponding lithium reagent and anhydrous zinc chloride in THF.
The crude reaction mixture was chromatographed on silica and eluted with 50%
CHZC12/hexane. ' H NMR (250 MHz, CDCl3) epsilon 9.25 (s, 1 H); 8.89 (m, 4H);
8.85 (d, 1 H,
J = 4.9); 8.76 (d, 1 H, J = 4.9); 8.16 (m, 6H); 8.09 (d, 2H, J = 7.1 ); 7.67
(m, 12H); 0.21 (s,
9H). Vis (CHC13) 431 (5.43), 523 (shoulder); (4.18), 598 (3.67).
D. 2-n-butyl-5,10,15,20-tetraphenyl porphyrinato zinc
Butyl zinc chloride was prepared from n-butyllithium and anhydrous zinc
chloride in
THF.
The crude reaction mixture was chromatographed on silica and eluted with 50%
CHzCl2/hexane. ' H NMR (250 MHz, CDCI,) epsilon 8.97 (m, 4H); 8.91 (d, 1 H, J
= 4.7); 8.77
(d, 1H, J = 4.7); 8.74 (s, 1H); 8.22 (m, 6H); 8.13 (d, 2H, J = 7.3); 7.77 (m,
12H); 2.81 (t, 2H, J
= 7.7); 1.83 (quint, 2H, J = 7.8); 1.30 (quint, 2H, J = 7.6); 0.91 (t, 3H, J =
8.2).
EXAMPLE 6
VINYLIC-BRIDGED PORPHYRINS AND THEIR POLYMERS
A. cis-Bis-1,2-[5-(10,15,20-triphenylporphyrinato) zinc]ethene
5-Bromo-10,15,20-triphenylporphyrinato zinc (0.2 mmol) and Pd(PPh3)4 (0.02
mmole) are dissolved in 25 ml dry, degassed THF. A solution of cis-bis(tri-n-
butyltin)ethene
(0.2 mmol) in 5 ml THF is added and the solution heated at reflux for 2 days.
The reaction is
quenched with water, extracted with methylene chloride, dried over calcium
chloride, and the
solvents are evaporated. The crude solid is chromatographed on silica using
methylene
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WO 02/104072 PCT/US02/05584
chloride/hexane eluant to isolate a dimer having formula (3), wherein R,q, ,
RA3 , and RA4 are
phenyl and M is Zn.
B. cis-Bis-1,2-[5-[10,15,20-tris(pentafluoro-phenyl)]-2,3,7,8,12,13,17,18-
octakis-
(trifluoromethyl) porphyrinato zinc]-1,2-difluoroethene
5-Bromo-10,15,20-tris(pentafluorophenyl)porphyrinato zinc (0.2 mmol) and
Pd(PPh3)4 (0.02 mmol) are dissolved in 25 ml dry THF. A solution of cis-
bis(tri-n-butyltin)-
1,2-difluoroethene (0.2 mmol) in 5 ml THF is added and the solution heated at
reflux for 2
days. The reaction is quenched with water, extracted with methylene chloride,
dried over
calcium chloride, and the solvents evaporated. The crude solid is
chromatographed on silica
using methylene chloride/hexanes eluent to isolate cis-bis-1,2-[5-[10,15,20-
tris(pentafluorophenyl)porphyrinato zinc]-1,2-difluoroethene.
This material is dissolved in chloroform and reacted with a large excess of N-
bromosuccinimide as in Example 2 to perbrominate positions RB,-RB8 on both
porphyrins.
The resulting material filtered through a fine fritted disk and washed with
water, methanol,
and acetone, dried in vacuo, and then recrystallized from THF/heptane. cis-Bis-
1,2-[5-
[10,15,20-tris(pentafluoro-phenyl)-2,3,7,8,12,13,17,18- octabromoporphyrinato
zinc is
reacted with Pd(dppfJ and a large excess of CuCF3 in the dark as in Example 4.
After a
reaction time of about 48 hours, the product is chromatographed on silica with
CHZC12/CCl4
eluent to yield the title compound.
C. Cofacial-bis-[cis-ethenyl meso-bridged]porphyrin[CEBP](Formula (5)) and
Polymeric-bis-[cis-ethenyl meso-bridged]porphyrin [PABP](Formula (6))
5,15-Dibromo=10,20-diphenylporphyrinato zinc (0.2 mmol) and Pd(PPh,)4 (0.02
mmole) are dissolved in 25 ml dry, degassed THF. A solution of cis-bis(tri-n-
butyltin)ethene
(0.2 mmol) in 5 ml THF is added and the solution heated at reflux for 2 days.
The reaction is
quenched with water, extracted with methylene chloride, dried over calcium
chloride, and the
solvents are evaporated. The crude solid is chromatographed on silica using
methylene
chloride/hexane eluant to isolate the Cofacial-bis-[cis-ethenyl meso-
bridged]zinc porphyrin
complex of formula (5) and Polymeric-bis-[cisethenyl meso-bridged] porphyrin
species of
formula (6), wherein RA, and R,q3 are phenyl and M is Zn.
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RA1
i i
/ N ~~~N \
1w
~A3
N~ ~N~~
N/N~N w
.~ ,-
Ra3
(5)
(6)
~~~~\
~ Ray
R M\N~\
A3
N\
RA, V \
N~ ~N~
i N/M\N w
D. Fluorinated Cofacial-bis-[cis-ethenyl mesobridged]porphyrin[FCEBP]and
Fluorinated
Polymeric-bis-[cis-ethenyl meso-bridged]porphyrin [FPEBP]
5,15-Dibromo-10,20-bis(pentafluorophenyl) porphyrinato zinc (0.2 mmol) and
Pd(PPh~)4 (0.02 mmol) are dissolved in 25 ml dry THF. A solution of cis-
bis(tri-n-butyltin)-
1,2-difluoroethene (0.02 mmol) in 5 ml THF is added and the solution heated at
reflux for 2
days. The reaction is quenched with water, extracted with methylene chloride,
dried over
calcium chloride, and the solvents evaporated. The crude solid is
chromatographed on silica
using methylene chloride/hexanes eluent to isolate the Cofacial-bis-
[cisethenyl meso-bridged]
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zinc porphyrin complex as well as the Polymeric-bis-[cis-ethenyl meso-bridged]
porphyrin
species. The cofacial and polymeric species are dissolved separately in
chloroform. The
cofacial porphyrin complex dissolved in chloroform and reacted with a large
excess of N-
bromosuccinimide as in Example 2 to perbrominate positions RB,-RB8 on both
porphyrins.
~ The resulting material filtered through a fme fritted disk and washed with
water, methanol,
and acetone, dried in vacuo, and then recrystallized from THF/heptane to yield
the title
compound. The isolated material is reacted with Pd(dppf) and a large excess of
CuCF, in the
dark in a manner as in Example 4. After a reaction time of about 48 hours, the
product is
chromatographed on silica with CHzCIz/CC14 eluent to yield a perfluorinated
CEPB analogous
to formula (S). Perfluorinated PEBP is synthesized in a similar manner,
yielding a species
analogous to formula (6) where highly fluorinated porphyrins are linked via
fluorovinyl units.
E. Cofacial-bis-[1,8-anthracenyl-meso-bridged]porphyrin [CBAP] (Formula (7))
and
Polymeric-bis-[1,8-anthracenyl-meso-bridged][PBAP]porphyrin (Formula (8))
5,15-Dibromoporphyrinato zinc (0.2 mmol) and Pd(PPh3)4 (0.02 mmol) are
dissolved
in 25 ml dry, degassed THF. A solution of 1,8-anthracenyl-bis-(tributyl tin)
(0.2 mmol) in 5
ml THF is added and the solution heated at reflux for 2 days. The reaction is
quenched with
water, extracted with methylene chloride, dried over calcium chloride, and the
solvents are
evaporated. The crude solid is chromatographed on silica using methylene
chloride/hexane
eluant to isolate the Cofacial-bis-[1,8-anthracenyl-meso-bridged]zinc
porphyrin complex of
formula (7) and the Polymeric-bis-[1,8-anthracenyl-meso-bridged]zinc porphyrin
species of
formula (8), where and RAl and RA3 are phenyl and M is Zn.
R
RA3
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a~, 1 (
10
EXAMPLE 7
ACETYLENIC PORPHYR1N POLYMERS
A. Poly(5,15-bis(ethynyl)-10,20-diphenylporphyrinato zinc)
5,15-Bis(ethynyl)-10,20-diphenylporphyrinato zinc (0.2 mmol) in pyridin (20
ml) is
slowly added to a solution of cupric acetate (0.4 mmol) in 20 ml 1:1
pyridine/methanol
generally according to the procedure of Eglinton, et al., The Coupling of
Acetylenic
Compounds, p. 311 in Advances in Organic Chemistry, Raphael, et al., eds.,
1963,
Interscience Publishers.
B. Poly(5,15-bis(ethynylphenyl)-10,20-diphenylporphyrinato zinc)
5,15-Diethynyl-10,20-diphenylporphinato zinc (0.2 mmol) and 1,4-dibromobenzene
are combined in a mixture of 30 ml toluene and 10 ml diisopropylamine. Cul
(0.4 mmol) and
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Pd(Ph3)4 (0.02 mmol) are added and the mixture is heated at 65° C. for
3 days. The crude
solid is washed with methanol and acetone and dried in vacuo.
Alternatively, the polymer is prepared from 1,4-diethynylbenzene and 5,15-
dibromo-
10,20-diphenylporphinato zinc via the identical procedure.
EXAMPLE 8
DOPED PORPHYRIN POLYMERS
5,15-Bis(ethynyl)-10,20-diphenylporphyrinato zinc is polymerized according to
the
general procedure provided by Skotheim, ed., Handbook of Conducting Polymers,
Volume 1,
pp. 405-437, Marcel Dekker, 1986 using a catalytic amount of MoCls, Me(CO)6,
WCIb, or
W(CO)S. The resultant polymer is then doped with an oxidant such as iodine or
SbFs.
EXAMPLE 9
Metalation of Brominated Porphyrins
Finely divided zinc metal was prepared generally according to the method of
Rieke (J.
Org. Chem. 1984, 49, 5280 and J. Org. Chem. 1988, 53, 4482) from sodium
naphthalide and
zinc chloride (0.18 mmol each) in THF. A solution of [5-bromo-10,20-
diphenylporphinato]zinc (100 mg, 0.17 mmol) dissolved in 40 mL THF was added
by syringe
to the zinc metal suspension, and the mixture was stirred at room temperature
overnight;
during this time all of the zinc metal dissolved. The ring-metalated porphyrin
is suitable for
palladium-catalyzed coupling with a variety of aryl and vinyl halides.
EXAMPLE 10
Palladium-Catalyzed Cross-Coupling with Ring-Metalated Porphyrins
5-[(10,20-Diphenylporphinato)zinc]zinc bromide(0.2 mmol) is prepared in 15 mL
of
THF as in Example 9 above and is placed in a dry 100 mL Schlenk tube. A
solution of 2-
iodothiophene (0.4 mmol) in 5 mL of THF is added via syringe. Pd(dppf) (3 mg)
is prepared
by stirring a suspension of Pd(dppf)Clz in THF over Mg turnings for 20 min.
and is
transferred into the reaction mixture by canula. The solution is stirred
overnight, quenched
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with aqueous ammonium chloride, extracted with CHZCIz, and dried over CaClz.
The solvent
is evaporated to dryness and chromatography is carried out with 1:1 CHzCl2 as
eluant. The
product, [5-(2-thiophenyl)-10,20-diphenylporphinato]zinc, elutes in one band
and is isolated
in 90% yield.
EXAMPLE 11
Polymerization with Ring-Metalated Porphyrin Derivatives
[5,15-Bis(zinc bromide)-10,20-diphenylporphinato]-zinc (0.2 mmol) is prepared
in 15
mL of THF as in Example 9 and is placed in a dry 100 mL Schlenk tube. A
solution of [5,15
dibromo-10,20-diphenylporphinato]zinc (0.2 mmol) in 15 mL of THF is added by
syringe.
Pd(dppf) (3 mg) is prepared by stirring a suspension of Pd(dppf)Clz in THF
over Mg turnings
for 20 min. and is transferred into the reaction mixture by canula. The
mixture is heated at
60° C for 3 days, cooled to room temperature and filtered through a
fine-fritted glass disk.
The filtered polymer is washed with hexane followed by methanol and dried in
vacuo.
EXAMPLE 12
Carbonylation of [5-Bromo-10,20-Diphenylporphinato]Zinc
5-[(10,20-Diphenylporphinato)zinc]magnesium bromide (0.2 mmol) is prepared in
15
mL of THF as in Example 9 and is placed in a dry 100 mL Schlenk tube. The
vessel is cooled
to 0° C and dry COZ gas is bubbled through the solution. The solution
is stirred for 1 h at
room temperature, quenched with 0.1 M HCI, extracted with CHZC12, and dried
over CaClz.
The solvent is evaporated to dryness and chromatography is carried out with
THF:CHZC12 as
eluant. Upon evaporation of the solvent [5-carboxy-10,20-
diphenylporphinato]zinc is isolated
in 85% yield.
EXAMPLE 13
Coupling on Unmetalated Porphyrin Derivatives
A. Using Organozinc Chloride Reagents
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Trimethylsilylacetylene (3 mmol) was deprotonated with n-butyl lithium (3
mmol) at -
78° C. in THF and warmed slowly to room temperature. Excess ZnCl2 (650
mg) in 5 mL of
THF was transferred into the solution via canula. Pd(dppf) (3 mg) was prepared
by stirring a
suspension of Pd(dppf)Cl2 in THF over Mg turnings for 20 min. and transferred
into the
solution by canula. The entire reaction mixture was transferred to a dry 100
mL Schlenk tube
containing 340 mg of 5,15-dibromo-10,20-diphenylporphyrin. The solution was
heated to 40°
C and left sealed overnight. TLC of the reaction mixture after 18 h shows a
mixture of
fluorescent products. The mixture was quenched with aqueous ammonium chloride,
extracted
with CHzCl2, and dried over CaClz. The solvent was evaporated to dryness and
chromatography was carried out with 1:1 CHZCIz:hexane as eluant. The majority
of the
material was collected in two bands which proved to be [5-(2-
trimethylsilylethynyl)-10,20-
diphenylporphinato]zinc and [5,15-bis (2-trimethylsilylethynyl) -10,20-
diphenylporphinato]-
zinc. The two products were isolated in 83% overall yield.
B. Using Organotrialkyltin Reagents
5,15-Dibromo-10,20-diphenylporphyrin is placed in a dry 100 mL Schlenk tube
and
dissolved in 30 mL of THF. A solution of vinyltributyltin (3 mmol) in 5 mL THF
is added to
the reaction mixture. Pd(dppf) (3 mg) is prepared by stirring a suspension of
Pd(dppfJClz in
THF over Mg turnings for 20 min. and is transferred into the reaction mixture
by canula. The
solution is stirred overnight, quenched with aqueous ammonium chloride,
extracted with
CHzCl2, and dried over CaCl2. The solvent is evaporated to dryness and
chromatography is
carried out with 1:1 CHzCl2:hexane as eluant. The product, 5,15-diphenyl-10,20-
divinylprophyrin, elutes in one band and is isolated in 90% yield.
EXAMPLE 14
Coupling on Dilithialated Porphyrin Derivatives
A solution of N,N"-dilithio-5,15-dibromo-10,20-diphenylporphyrin (0.2 mmol) in
1 S
mL of THF is prepared generally according to the method of Arnold, J. Chem.
Soc. Commun.
1990, 976. A solution of vinyltributyltin (2 mmol) in 5 mL THF is added to the
reaction
mixture. Pd(dppfJ (3 mg) is prepared by stirring a suspension of Pd(dppfJCl2
in THF over Mg
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turnings for 20 min. and is transferred into the reaction mixture by canula.
The solution is
stirred overnight, and quenched with a solution of anhydrous NiClz in THF.
Aqueous
ammonium chloride is added, the solution is extracted with CHZC12, and dried
over CaCI,.
The solvent is evaporated to dryness and chromatography is carried out with
1:1
CHZCl2:hexane as eluant. The product, [5,15-diphenyl-10,20-
divinylporphinato]nickel, elutes
in one band and is isolated in 90% yield.
EXAMPLE 15
Bis[(5,5',-10,20-diphenylporphinato)zinc(II)]ethyne.
Lithium bistrimethylsilylamide (1 mmol) was added to a solution of (5-ethynyl-
10,20-
diphenylporphinato)zinc(II) (50 mg, 0.1 mmol) in 20 ml THF to yield the (5-
ethynyllithium-
10,20-diphenylporphinato)zinc(II) reagent. (5-bromo-10,20-
diphenylporphinato)zinc(II) (60
mg, 0.1 mmol) and 10 mg of Pd(PPh3)4 in 20 ml THF were added to this solution
by canula.
After completion of the metal-mediated cross-coupling reaction, chromatography
was carried
out on silica by using 9:1 hexane:THF as eluent. The first green band was
isolated and
evaporated to yield 77.2 mg of the product (yield = 72%, based on (5-ethynyl-
10,20-
diphenylporphinato)zinc(II)). 1H NMR (250 MHz, CDCl3):0 10.43 (d, 4 H, J= 4.6
Hz),
10.03 (s, 2 H), 9.21 (d, 4 H, J = 4.4 Hz), 9.06 (d, 4 H, J = 4.5 Hz), 8.91 (d,
4 H, J = 4.4 Hz),
8.22 (m, 8 H), 7.72 (m, 12 H). Vis (CHCl3) 413.9 (4.96), 420.5 (4.97), 426.0
(4.96), 432.6
(4.92), 445.8 (4.89), 477.7 (5.1), 549.2 (4.15), 552.5 (4.14), 557.8 (4.15),
625.1 (4.09), 683.4
(4.37). FAB MS: 1070 (calcd 1070).
EXAMPLE 16
5,15-Bis[[(5'-10,20-diphenylporphinato)zinc(II)]ethynyl]-
[10,20-diphenylporphinato]zinc(II)
Pd(PPh3)4 (20 mg, 0.0173 mmol) and CuI (10 mg) were added to a solution of (5-
bromo-10,20-diphenylporphinato)zinc(II) (120 mg, 0.2 mmol) in 20 ml THF. (5,15-
diethynyl-10,20-diphenylporphinato)zinc(II) (57 mg, 0.1 mmol) and 0.35 ml of
diethylamine
in 20 ml THF were added to this solution by canula. After completion of the
metal-mediated
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cross-coupling reaction, the precipitated product was isolated via filtration
and then
recrystalized from a pyridine-hexane mixture to give 66.5 mg of the product
(yield = 41
based on the (5,15-diethynyl-10,20-diphenylporphinato)zinc(II) starting
material). 1H NMR
(S00 MHz, CDC13):0 10.86 (d, 4 H, J= 4.5 Hz), 10.78 (d, 4 H, J= 4.4 Hz), 10.39
(s, 2 H),
9.50 (d, 4 H, J = 4.3 Hz), 9.42 (d, 4 H, J = 4.4 Hz), 9.32 (d, 4 H, J = 4.8
Hz), 9.1 S (d, 4 H, J =
4.0 Hz),8.52 (m, 4H), 8.47 (m, 8 H), 7.89 (m, 6 H), 7.85 (m, 12 H). Vis (10:1
CHCl3:pyridine): 420.5 (4.84), 437.0 (4.72), 457.2 (4.66), 464.5 (4.66), 490.9
(4.85), 500.8
(4.95), 552.0 (3.99), 802.2(4.63). FAB MS: 1616 (calcd 1616).
EXAMPLE 17
The following is a general procedure for the preparation of a conjugated
compound
composed of at least two covalently bound moieties in which the composite
conjugated
compound emits in the 650-2000 nm wavelength domain and possesses an emission
dipole
strength that is large with respect to the either of the covalently bound
moieties (or
alternatively, the sum of the emission dipole strength of each of the two
covalently bound
moieties).
A known fluorophore, lumophore, or phosphore which is known to emit light at a
wavelength greater than or equal to 450 nm when optically or electrically
pumped, is
halogenated on its conjugated framework at a position that defines, or is
spatially close to,
either the head or tail of the lowest energy transition dipole. Those skilled
in the art will
recognize that experimental techniques such as pump-probe transient anisotropy
measurements, can be utilized to determine the orientation of the lowest
energy transition
dipole on the molecular reference frame.
This halogenated fluorophore, lumophore, or phosphore is now subjected to a
metal
catalyzed cross-coupling reaction which results in the formation of an ethyne
bond at the
atomic position that bore the above said halogen moiety.
This ethynylated fluorophore, lumophore, or phosphore is now subjected to a
second
metal-catalyzed cross-coupling reaction with the above said halogenated
fluorophore,
lumophore, or phosphore under conditions appropriate to produce an ethyne-
bridged
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bis(fluorophore, lumophore, or phosphore) compound, in which the ethyne moiety
connects
the two component emissive moieties along a vector that is defined by, or
approximates, the
head-to-tail alignment of their two respective transition dipoles.
Those skilled in the art will recognize that a known fluorophore, lumophore,
or
phosphore which is known to emit light at a wavelength greater than or equal
to 450 nm when
optically or electrically pumped, can be dihalogenated on its conjugated
framework at the
positions that define the head and tail of the lowest energy transition
dipole. This species can
be subjected to a metal-catalyzed cross-coupling reaction which results in the
formation of
ethyne bonds at the two atomic position that bore the above said halogen
moieties.
Those skilled in the art will recognize that a combination of halogenated,
dihalogenated, ethynylated, and diethynylated fluorophores, phosphores, or
lumophores will
enable the straightforward synthesis of dimeric, trimeric, tetrameric, and
oligomeric species
in which ethyne or butadiyne groups link the respective emissive units in a
manner which
provides head-to-tail alignment, or approximate head-to-tail alignment, of the
low energy
transition dipoles of the individual covalently bound moieties that comprise
the conjugated
compound.
EXAMPLE 18
In the following examples, all manipulations were carried out under nitrogen
previously passed through an 02 scrubbing tower (Schweitzerhall R3-11
catalyst) and a
drying tower (Linde 3-~ molecular sieves) unless otherwise stated. Air
sensitive solids were
handled in a Braun 150-M glove box. Standard Schlenk techniques were employed
to
manipulate air-sensitive solutions. CH2C12 and tetrahydrofuran (THF) were
distilled from
CaH2 and K/4-benzoylbiphenyl, respectively, under N2. N,N-Dimethylformamide
(DMF)
and benzonitrile were dried respectively over MgS04 and P205, and distilled
under reduced
pressure. All NMR solvents were used as received. ZnCl2 was dried by heating
under
vacuum and stored under N2. The catalysts Pd(PPh3)4 and
tris(dibenzylideneacetone)dipalladium(0) (Pd2dba3), as well as triphenylarsine
(AsPh3) were
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purchased from Strem Chemicals and used as received. Meso-
heptafluoropropyldipyrrylmethane ((a) Wijesekera, T. P. Can. J. Chem. 1996,
74, 1868-1871
(b) Nishino, N.; Wagner, R. W.; Lindsey, J. S. J. Org. Chem. 1996, 61, 7534-
7544) and
trimethylsilylpropynal (Kruithof, K. J. H.; Schmitz, R. F.; Klumpp, G. W.
Tetrahedron 1983,
39, 3073-3081) were prepared according to the published procedures. The
supporting
electrolyte used in the electrochemical experiments, tetra-n-butylammonium
hexafluorophosphate, was recrystallized two times from ethanol and dried under
vacuum at
70 °C overnight prior to use.
Chemical shifts for 1H NMR spectra are relative to tetramethylsilane (TMS)
signal in
the deuterated solvent (TMS, 8 = 0.00 ppm), while those for 19F NMR spectra
are referenced
to fluorotrichloromethane (CFC13, 8 = 0.00 ppm). All J values are reported in
Hertz. Flash
and size exclusion column chromatography were performed on the bench top,
using
respectively silica gel (EM Science, 230-400 mesh) and Bio-Rad Bio-Beads SX-1
as media.
Mass spectra were acquired at the Mass Spectrometry Center at the University
of
Pennsylvania. MALDI-TOF mass spectroscopic data were obtained with a
Perspective
Voyager DE instrument in the Laboratory of Dr. Virgil Percec (Department of
Chemistry,
University of Pennsylvania). Samples were prepared as micromolar solutions in
THF, and
dithranol (Aldrich) was utilized as the matrix.
Instrumentation. Electronic spectra were recorded on an OLIS UV/vis/near-IR
spectrophotometry system that is based on the optics of a Cary 14
spectrophotometer.
Emission spectra were recorded on a SPEX Fluorolog luminescence spectrometer
that
utilized a T-channel configuration and PMT/InGaAs/Extended-InGaAs detectors;
these
spectra were corrected using a calibrated light source supplied by the
National Bureau of
Standards. NMR spectra were recorded on either 200 MHz AM-200, 250 MHz AC-250,
or
500 MHz AMX-500 Bruker spectrometers. Cyclic voltammetric measurements were
carried
out on an EG&G Princeton Applied Research model 273A Potentiostat/Galvanostat.
The
electrochemical cell used for these experiments utilized a platinum disk
working electrode, a
platinum wire counter electrode, and a saturated calomel reference electrode
(SCE). The
reference electrode was separated from the bulk solution by a junction bridge
filled with the
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corresponding solvent/supporting electrolyte solution. The
ferrocene/ferrocenium redox
couple was utilized as an internal potentiometric standard.
All electronic structure calculations were carried out using the GAUSSIAN 98
programs (Frisch, et al.,. Gaussian 98, Revision A.9; Gaussian, Inc:
Pittsburgh, PA, 1998.
Geometry optimizations were performed using the semiempirical PM3 method. In
order to
minimize computational effort, the solubilizing phenyl substituents of the
tris[(porphinato)zinc(II)] structures were replaced by hydrogen atoms, while
C3F~ groups
were replaced by C2F5. The models for the conjugated DDD and DAD
tris[(porphinato)zinc(II)] compounds were optimized respectively within D2h
and CZh
symmetry constraints.
9-Methoxy-1,4,7-trioxanonyltosylate (1). p-Toluenesulfonyl chloride (17.69 g,
9.28 x
10-2 mol) was dissolved in 50 ml of dry pyridine and cooled to -5 nC.
Triethylene glycol
monomethyl ether (13.50 ml, 8.44 x 10-2 mol) was added dropwise to the
solution, and the
reaction mixture was stirred under N2 for 4 h at -5 L7C. The reaction mixture
was poured
onto ice and extracted three times with CH2C12. The combined organic layers
were washed
with 6M HCI, saturated aq. NaCI, and dried over Na2S04. The solvent was
evaporated to
give a viscous oil. Yield = 26.09 g (97%, based on 13.50 ml of triethylene
glycol monomethyl
ether). 1H NMR (250 MHz, CDCl3): 8 7.80 (d, 2H, J = 8.2 Hz, Ph-H), 7.35 (d,
2H, j = 8.2 Hz,
Ph-H), 4.16 (t, 2H, J = 4.8 Hz, -O-CH2-C), 3.69 (t, 2H, J = 4.8 Hz, -O-CH2-C),
3.61 (m, 6H, -O-
CH2-C), 3.53 (m, 2H, -O-CH2-C), 3.38 (s, 3H, -OCH3), 2.45 (s, 3H, -CH3). CI MS
m/z : 319
[(M+H)+] (calcd 319).
3,5-Bis(9-methoxy-1,4,7-trioxanonyl)benzaldehyde (2). 3,5-
Dihydroxybenzaldehyde (3.052 g, 2.21 x 10-2 mol), K2C03 (9.00 g, 6.51 x 10-2
mol) and 60
ml of dry DMF were added to a two-neck 200 ml flask, and the mixture stirred
under N2. A
solution of 1 (16.53 g, 5.19 x 10-2 mol) in 40 ml of dry DMF was added to the
reaction
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mixture, following which it was refluxed for 1 h, cooled, diluted with 100 ml
H20, and
extracted several times with CH2C12. The combined organic layers were washed
with
water, saturated aq. NaCI, and dried over Na2S04. After the solvent was
evaporated, the
residue was chromatographed on silica gel using 50:1 CH2C12:MeOH as the
eluent. Yield =
6.779 g (71 %, based on 3.052 g of 3,5-dihydroxybenzaldehyde). 1H NMR (250
MHz, CDCl3):
S 9.88 (s,1H, -CHO), 7.02 (d, 2H, J = 2.3 Hz, o-Ph-H), 6.76 (t,1H, J = 2.3 Hz,
p-Ph-H), 4.16 (m,
4H, -O-CH2-C), 3.87 (m, 4H, -O-CH2-C), 3.75 (m, 4H, -O-CH2-C), 3.67 (m, 8H, -O-
CH2-C),
3.56 (m, 4H, -O-CH2-C), 3.38 (s, 6H, -OCH3). CI MS m/z : 431 [(M+H)+] (calcd
431).
5,15-Bis[3,5-bis(9-methoxy-1,4,7-trioxanonyl)phenyl]porphyrin (3). 2,2'-
Dipyrrylmethane (2.29 8,1.57 x 10-2 mol) and 2 (6.70 8,1.56 x 10-2 mol) were
dissolved in
2.7 L of dry CH2C12. The solution was purged with N2 for 20 min before
trifluoroacetic acid
(0.30 ml, 3.89 x 10-3 mol) was added via syringe. The reaction mixture was
stirred for 17 h
at room temperature in the dark under N2. DDQ (5.35 g, 2.36 x 10-2 mol) was
then added to
the reaction mixture, and the solution stirred for an additional 2 h. The
solvent was
evaporated, and the residue chromatographed on silica gel using 30:1
CH2C12:MeOH as the
eluent. Yield = 2.820 g (33%, based on 6.70 g of 2). 1H NMR (250 MHz, CDC13):
810.31 (s,
2H, meso-H), 9.38 (d, 4H, J = 4.6 Hz, 8 -H), 9.15 (d, 4H, J = 4.7 Hz, b -H),
7.46 (d, 4H, J = 2.2
Hz, o-Ph-H), 6.97 (t, 2H, J = 2.2 Hz, p-Ph-H), 4.34 (m, 8H, -O-CH2-C), 3.96
(m, 8H, -O-CH2-
C), 3.79 (m, 8H, -O-CH2-C), 3.71 (m, 8H, -O-CH2-C), 3.64 (m, 8H, -O-CH2-C),
3.50 (m, 8H, -
O-CH2-C), 3.32 (s,12H, -OCH3), -2.03 (s, 2H, N-H). Vis (CH2C12): ~.max 407,
504, 537, 573,
629 nm. ESI MS m/z :1133.5267 [(M+Na)+] (calcd for C6pH78N40161133.5310).
5,15-Dibromo-10,20-bis[3,5-bis(9-methoxy-1,4,7-trioxanonyl)phenyl]porphyrin
(4).
Compound 3 (2.655 g, 2.39 x 10-3 mol) was dissolved in 300 ml of chloroform
and cooled to
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-5 ~C. Pyridine (2.0 ml) and N-bromosuccinimide (0.893 g, 5.02 x 10-3 mol)
were added
directly to the reaction mixture, and the reaction was followed by TLC (30:1
CHCI3:MeOH).
After 20 min, the reaction mixture was poured into water; the organic layer
was separated,
dried over Na2S04, and evaporated. The residue was chromatographed on silica
gel using
30:1 CHCI3:MeOH as the eluant. Yield = 2.950 g (97%, based on 2.655 g of the
porphyrin
starting material). 1H NMR (250 MHz, CDCl3): 8 9.60 (d, 4H, J = 4.9 Hz, (3-H),
8.92 (d, 4H, J
= 4.9 Hz, (3-H), 7.35 (d, 4H, J = 2.3 Hz, o-Ph-H), 6.95 (t, 2H, J = 2.2 Hz, p-
Ph-H), 4.31 (m, 8H, -
O-CH2-C), 3.95 (m, SH, -O-CH2-C), 3.78 (m, 8H, -O-CH2-C), 3.70 (m, 8H, -O-CH2-
C), 3.63
(m, 8H, -O-CH2-C), 3.50 (m, 8H, -O-CH2-C), 3.32 (s,12H, -OCH3), -2.44 (s, 2H,
N-H). Vis
(CH2C12): ~.max 424, 520, 556, 599, 658 nm. ESI MS m/z :1289.3452 [(M+Na)+]
(calcd for
1289.3520).
(5,15-Dibromo-10,20-bis[3,5-bis(9-methoxy-1,4,7-
trioxanonyl)phenyl]porphinato)zinc(II) (5). Compound 4 (2.856 g, 2.25 x 10-3
mol) was
dissolved in 200 ml of chloroform and refluxed. Zinc acetate dehydrate (1.23
g, 5.60 x 10-3
mol) in 50 ml of methanol was gradually added, and the reaction mixture was
refluxed for
an additional 2 h. After cooling to an ambient temperature, the solvent was
evaporated, and
the residue chromatographed on silica gel using 30:1 CHCI3:MeOH as the eluent.
Yield =
2.914 g (97%, based on 2.856 g of the porphyrin starting material). 1H NMR
(250 MHz,
CDCl3): 8 9.68 ~(d, 4H, J = 4.7 Hz, ~3 H), 8.98 (d, 4H, J = 4.7 Hz, ,a H),
7.45 (d, 4H, J = 2.3 Hz, o-
Ph-H), 6.92 (t, 2H, J = 2.2 Hz, p-Ph-H), 4.32 (m, 8H, -O-CH2-C), 3.88 (m, 8H, -
O-CH2-C), 3.65
(m, 8H, -O-CH2-C), 3.48 (m, 8H, -O-CH2-C), 3.03 (m, 8H, -O-CH2-C), 2.76 (m,
8H, -O-CH2-
C), 2.58 (s,12H, -OCH3). Vis (CH2C12): fax 426, 559, 601 nm. ESI MS m/z :
1351.2683
[(M+Na)+] (calcd for 1351.2656).
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(5,15-Bis[trimethylsilylethynyl]-10,20-bis[3,5-bis(9-methoxy-1,4,7-
trioxanonyl)phenyl]porphinato)zinc(II) (6). Dry THF (20 mL) and
(trimethylsilyl)acetylene
(0.36 ml, 2.5 x 10-3 mol) were added to a 100 mL Schlenk tube, cooled to -78
OC, and stirred.
Methyl lithium (1.4 M solution in diethyl ether,1.80 ml, 2.52 x 10-3 mol) was
added to the
solution; after stirring for 30 min, the solution was warmed to room
temperature, and ZnCl2
(0.734 g, 5.39 x 10-3 mol) in 30 ml of dry THF was transferred into the
reaction mixture and
stirred for 10 min. This solution was canula transferred under N2 to a Schlenk
tube
containing 5 (0.224 8,1.68 x 10-4 mol) and Pd(PPh3)4 (0.031 g, 2.7 x 10-5 mol)
in 30 ml of dry
THF, and stirred at 60 f~C for 16 h. The reaction mixture was then quenched
with water and
extracted with CHC13, following which the organic layer was washed with water,
dried
over CaCl2, and evaporated. The crude product was chromatographed on silica
gel using
30:1 CH2C12:MeOH as the eluent. Yield = 0.206 g (90%, based on 0.224 g of the
porphyrin
starting material). 1H NMR (250 MHz, CDCl3): 8 9.62 (d, 4H, j = 4.6 Hz, ,l3
H), 8.93 (d, 4H, J
= 4.7 Hz, ,j-H), 7.41 (d, 4H, J = 2.2 Hz, o-Ph-H), 6.89 (t, 2H, J = 2.2 Hz, p-
Ph-H), 4.29 (m, 8H, -
O-CH2-C), 3.86 (m, 8H, -O-CH2-C), 3.65 (m, 8H, -O-CH2-C), 3.49 (m, SH, -O-CH2-
C), 3.12
(m, 8H, -O-CH2-C), 2.89 (m, 8H, -O-CH2-C), 2.71 (s,12H, -OCH3), 0.61 (s,18H, -
Si-CH3).
Vis (CH2C12): ~.max (log e) 437 (5.56), 578 (4.05), 629 (4.39) nm. ESI MS m/z
:1387.5280
[(M+Na)+] (calcd for 1387.5236).
(5,15-Diethynyl-10,20-bis[3,5-bis(9-methoxy-1,4,7-
trioxanonyl)phenyl]porphinato)zinc(II) (7). Tetrabutylammonium fluoride (1 M
in THF,
0.34 ml, 3.4 x 10-4 mol) was added to a solution of 6 (0.156 8,1.14 x 10-4
mol) in 30 ml of
CH2C12 under N2. The solution was extracted with water, dried over CaCl2, and
evaporated. The residue was chromatographed on silica gel using 25:1
CHCI3:MeOH as the
eluent. Yield = 0.108 g (77%, based on 0.156 g of the porphyrin starting
material). 1H NMR
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(250 MHz, CDC13): 8 9.67 (d, 4H, J = 4.5 Hz, ~3 H), 8.97 (d, 4H, J = 4.5 Hz,
~H), 7.44 (d, 4H, J
= 2.2 Hz, o-Ph-H), 6.90 (t, 2H, J = 2.1 Hz, p-Ph-H), 4.29 (m, 8H, -O-CH2-C),
3.86 (m, 8H, -O-
CH2-C), 3.65 (m, 8H, -O-CH2-C), 3.49 (m, 8H, -O-CH2-C), 3.12 (m, 8H, -O-CH2-
C), 2.89 (m,
8H, -O-CH2-C), 2.71 (s,12H, -OCH3), 0.61 (s,18H, -Si-CH3). Vis (CH2C12):
7,,max 429, 558,
609 nm. ESI MS m/z : 1243.4413 [(M+Na)+] (calcd for 1243.4445).
3,3-Dimethyl-1-butyltosylate (8). p-Toluenesulfonyl chloride (17.35 g, 9.10 x
10-2
mol) was dissolved in 50 ml of dry pyridine and cooled to 0 OC. 3,3-Dimethyl-1-
butanol
(11.0 ml, 9.10 x 10-2 mol) was added dropwise, and the mixture was stirred
under N2 at 0
~C for 4 h, following which it was poured onto ice, and extracted three times
with CH2Cl2.
The combined organic layers were washed twice with 6 M HCI, saturated aq.
NaHC03,
saturated aq. NaCI, and dried over MgS04. The solvent was evaporated at room
temperature to give a viscous oil. Yield = 23.063 g (99%, based on 11.0 ml of
3,3-dimethyl-1-
butanol). 1H NMR (250 MHz, CDCl3): 8 7.80 (d, 2H, J = 8.3 Hz, Ph-H), 7.35 (d,
2H, J = 8.1
Hz, Ph-H), 4.09 (t, 2H, J = 7.4 Hz, -O-CH2-C), 2.46 (s, 3H, -CH3),1.58 (t, 2H,
J = 7.4 Hz, -OC-
CH2-C), 0.87 (s, 9H, -C-CH3). CI MS m/z : 257 [(M+H)+] (calcd for 257).
3,5-Bis(3,3-dimethyl-1-butyloxy)benzaldehyde (9). 3,5-Dihydroxybenzaldehyde
(4.008 g, 2.90 x 10-2 mol), K2C03 (8.016 g, 5.80 x 10-2 mol) and 50 ml of dry
DMF were
stirred in a 100 mL round-bottom flask under N2. Compound 8 (14.869 g, 5.80 x
10-2 mol)
was added, and the solution was heated at 80 fJC for 13 h. The reaction
mixture was then
cooled, filtered, and evaporated, following which water was added to the
residue, and the
aqueous mixture extracted three times with CHC13. The combined organic layers
were
washed with 2% HCl solution, aq. NaHC03, aq. NaCI, and dried over MgS04. After
removal of volatiles, the residue was chromatographed on silica gel with
CHCl3. Yield =
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7.314 g (82%, based on 4.008 g of 3,5-dihydroxybenzaldehyde). 1H NMR (250 MHz,
CDCl3):
8 9.85 (s,1H, -CHO), 6.98 (d, 2H, J = 2.3 Hz, o-Ph-H), 6.68 (t,1H, J = 2.3 Hz,
p-Ph-H), 4.04 (t,
4H, J = 7.3 Hz, -O-CH2-C),1.74 (t, 4H, J = 7.3 Hz, -OC-CH2-C),1.00 (s,18H, -C-
CH3). CI MS
m/z : 307 [(M+H)+] (calcd 307).
5,15-Bis[3',5'-di(3,3-dimethyl-1-butyloxy)phenyl]porphyrin (10). 2,2'-
Dipyrrylmethane (1.604 8,1.10 x 10-2 mol) and 9 (3.342 8,1.09 x 10-2 mol) were
dissolved in
2.1 L of dry CH2C12. The solution was purged with N2 for 20 min, following
which
trifluoroacetic acid (0.19 ml, 2.47 x 10-3 mol) was added via syringe. The
reaction mixture
was stirred in the dark for 22 h at room temperature under N2. DDQ (3.70
8,1.63 x 10-2
mol) was then added, and the reaction mixture was stirred for an additional h.
The solvent
was evaporated, and the residue chromatographed on silica gel using CH2C12 as
the eluent.
Yield = 2.234 g (47%, based on 3.342 g of 9). 1H NMR (250 MHz, CDC13): 810.31
(s, 2H,
meso-H), 9.39 (d, 4H, J = 4.7 Hz, ~i-H), 9.19 (d, 4H, J = 4.7 Hz, (3-H), 7.43
(d, 4H, J = 2.3 Hz, o-
Ph-H), 6.91 (t, 2H, J = 2.2 Hz, p-Ph-H), 4.21 (t, 8H, J = 7.4 Hz, -O-CH2-
C),1.86 (t, 8H, J = 7.4
Hz, -OC-CH2-C),1.00 (s, 36H, -C-CH3), -2.06 (s, 2H, N-H). Vis (CH2C12): 7~,max
408, 503,
535, 574, 628 nm. ESI MS m/z : 863.5494 [(M+H)+] (calcd 863.5476).
5-Bromo-10,20-bis[3',5'-bis(3,3-dimethyl-1-butyloxy)phenyl]porphyrin (11).
Compound 10 (1.667 8,1.93 x 10-3 mol) was dissolved in 300 ml of CHC13 and
cooled to -5
nC. Pyridine (2 mL) and N-bromosuccinimide (0.345 8,1.94 x 10-3 mol) were then
added,
and the reaction was followed by TLC. After 15 min, the reaction mixture was
poured into
water; the organic layer was separated, dried over Na2S04, filtered, and
evaporated. The
residue was chromatographed on silica gel using 3:2 CHCl3:hexanes as the
eluent. Two
products were recovered: 5,15-dibromo-10,20-bis[3',5'-bis(3,3-dimethyl-1-
butyloxy)phenyl]porphyrin (0.390 g, 20%) and the target compound (1.058 g,
58%, based on
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1.667 g of the porphyrin starting material). 1H NMR (250 MHz, CDC13): 810.16
(s,1H,
meso-H), 9.73 (d, 2H, j = 4.9 Hz, ,(~H), 9.28 (d, 2H, J = 4.6 Hz, ~-H), 9.08
(d, 2H, J = 4.7 Hz, /~
H), 9.07 (d, 2H, J = 4.8 Hz, /j-H), 7.37 (d, 4H, J = 2.1 Hz, o-Ph-H), 6.90 (t,
2H, J =1.8 Hz, p-Ph-
H), 4.20 (t, 8H, J = 7.4 Hz, -O-CH2-C),1.85 (t, SH, j = 7.4 Hz, -OC-CH2-
C),1.00 (s, 36H, -C-
CH3), -2.20 (s, 2H, N-H). Vis (CH2C12): 7~max 417, 511, 544, 587, 644 nm. ESI
MS m/z
941.4597 [(M+H)+] (calcd 941.4580).
(5-Bromo-10,20-bis[3',5'-bis(3,3-dimethyl-1-
butyloxy)phenyl]porphinato)zinc(II)
(12). Compound 11 (1.315 8,1.40 x 10-3 mol) was dissolved in 150 ml of CHCl3
and
refluxed. Zinc acetate dihydrate (0.770 g, 3.51 x 10-3 mol) in 25 ml of
methanol was added
gradually, and the reaction mixture was refluxed for 2 h. After cooling and
removal of
volatiles, the residue was chromatographed on silica gel using 15:1
hexanes:THF as the
eluent. Yield =1.348 g (96%, based on 1.315 g of the porphyrin starting
material). 1H NMR
(250 MHz, CDCl3): 810.23 (s,1H, meso-H), 9.81 (d, 2H, J = 4.8 Hz, ,l~H), 9.37
(d, 2H, J = 4.6
Hz, ~H), 9.18 (d, 2H, J = 4.6 Hz, /~H), 9.17 (d, 2H, J = 4.7 Hz, /3-H), 7.38
(d, 4H, J = 2.2 Hz, o-
Ph-H), 6.90 (t, 2H, j = 2.2 Hz, p-Ph-H), 4.19 (t, 8H, J = 7.4 Hz, -O-CH2-
C),1.85 (t, 8H, J = 7.4
Hz, -OC-CH2-C),1.00 (s, 36H, -C-CH3). Vis (CH2C12): Amax 418, 547, 580 nm. ESI
MS m/z
1002.3601 (M+) (calcd 1002.3638).
(5-Trimethylsilylethynyl-10,20-bis[3',5'-bis(3,3-dirnethyl-1-
butyloxy)phenyl]porphinato)zinc(II) (13). THF (20 ml) and
(trimethylsilyl)acetylene (0.56
ml, 3.96 x 10-3 mol) were added to a 100 mL Schlenk tube, stirred, and cooled
to -78 f 7C.
Methyl lithium (1.4 M solution in diethyl ether, 2.90 ml, 4.06 x 10-3 mol) was
added, and the
solution stirred for 30 min. After warming to room temperature, ZnCl2 (1.095
g, 8.03 x 10-3
mol) in 50 ml of dry THF was transferred to the reaction mixture by canula.
After stirring
for 10 min, the reaction mixture was transferred to a 250 mL Schlenk tube
containing 12
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(0.404 g, 4.02 x 10-4 mol) and Pd(PPh3)4 (0.069 g, 5.97 x 10-5 mol) and 40 ml
of dry THF.
The mixture was stirred under N2 at 60 ~C for 16 h, following which it was
quenched with
water, extracted with CH2C12, washed with water, dried over CaCl2, and
evaporated. The
crude product was chromatographed on silica gel using 10:1 hexanes:THF as the
eluent.
Yield = 0.404 g (98%, based on 0.404 g of the porphyrin starting material). 1H
NMR (250
MHz, CDC13): 810.18 (s,1H, meso-H), 9.78 (d, 2H, J = 4.5 Hz, ,(~H), 9.33 (d,
2H, J = 4.5 Hz,H),
9.14 (d, 2H, J = 4.7 Hz, ,(3 H), 9.13 (d, 2H, J = 4.5 Hz, ~fH), 7.37 (d, 4H, J
= 2.2 Hz, o-Ph-H),
6.88 (t, 2H, j = 2.2 Hz, p-Ph-H), 4.19 (t, 8H, J = 7.4 Hz, -O-CH2-C),1.84 (t,
8H, J = 7.4 Hz, -
OC-CH2-C),1.00 (s, 36H, -C-CH3), 0.62 (s, 9H, -Si-CH3). Vis (CH2Cl2): 7~ax
(log E) 427
(5.51), 554 (4.15), 594 (3.70) nm. ESI MS m/2 : 1021.5013 [(M+H)+] (calcd
1021.5005).
(5-Ethynyl-10,20-bis[3',5'-bis(3,3-dimethyl-1-
butyloxy)phenyl]porphinato)zinc(II)
(14). Tetrabutylammonium fluoride (1 M in THF, 0.73 ml, 7.3 x 10-4 mol) was
added to a
solution of 13 (0.375 g, 3.67 x 10~ mol) in 40 ml of CH2C12 under N2. The
reaction mixture
was stirred for 10 min, quenched with water, extracted with CH2C12~ and dried
over CaCl2.
After the solvent was evaporated, the residue was chromatographed on silica
gel using 10:1
hexanes:THF as the eluent. Yield 0.340 g (97%, based on 0.375 g of the
porphyrin starting
material). 1H NMR (250 MHz, CDC13): 810.22 (s,1H, meso-H), 9.79 (d, 2H, J =
4.7 Hz, ~3 H),
9.35 (d, 2H, J = 4.5 Hz, ~H), 9.17 (d, 2H, J = 4.7 Hz, ~H), 9.15 (d, 2H, J =
4.6 Hz, ~H), 7.37
(d, 4H, J = 2.2 Hz, o-Ph-H), 6.88 (t, 2H, J = 2.6 Hz, p-Ph-H), 4.18 (t, 8H, J
= 7.4 Hz, -O-CH2-C),
4.15 (s,1H, -CC-H),1.84 (t, SH, J = 7.4 Hz, -OC-CH2-C),1.00 (s, 36H, -C-CH3).
Vis
(CH2C12): 7~,max 422, 552, 590 nm. ESI MS m/z : 949.4595 [(M+H)+] (calcd
949.4611).
Bis[(5,5'-10,20-bis[3,5-bis(3,3-dimethyl-1-
butyloxy)phenyl]porphinato)zinc(II)]ethyne (DD). Compounds 12 (0.0696 g, 6.92
x 10-5
mol) and 14 (0.066 g, 6.94 x 10-5 mol), 20 ml of dry THF, and 2.0 ml of
triethylamine were
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added to a 50 mL Schlenk tube. Pd2(dba)3 (0.019 g, 2.07 x 10-5 mol) and AsPh3
(0.051 g,
1.67 x 10-4 mol) were transferred to the Schlenk tube in a dry box, following
which the
solution was degassed by three successive freeze-pump-thaw cycles. The
reaction mixture
was stirred at 45 f~C for 10.5 h, after which time the solvent was evaporated,
and the residue
chromatographed on silica gel using 10:1 hexanes:THF as the eluent. Yield =
0.115 g (89%,
based on 0.0696 g of 12). 1H NMR (250 MHz, CDCl3): 810.48 (d, 4H, J = 4.7 Hz,
~H),10.19
(s, 2H, meso-H), 9.37 (d, 4H, J = 4.4 Hz, /.~H), 9.35 (d, 4H, J = 4.5 Hz, ~3
H), 9.19 (d, 4H, J = 4.5
Hz, /~H), 7.46 (d, 8H, J = 2.2 Hz, o-Ph-H), 6.91 (t, 4H, J = 2.2 Hz, p-Ph-H),
4.22 (t,16H, J = 7.4
Hz, -O-CH2-C),1.86 (t,16H, J = 7.4 Hz, -OC-CH2-C),1.01 (s, 72H, -C-CH3). Vis
(CH2C12):
Amax (log s) 399 (5.06), 404 (5.06), 426 (5.03), 439 (4.96), 476 (5.42), 539
(4.19), 558 (4.23), 669
(4.62) nm. MALDI-TOF MS m/z :1871.65 (M+) (calcd 1870.8906).
[(5, 10,20-bis[3,5-bis(3,3-dimethyl-1-butyloxy)phenyl]porphinato)zinc(II)]-
[(5', 15'-
bromo-10',20'-bis[3,5-bis(3,3-dimethyl-1-
butyloxy)phenyl]porphinato)zinc(II)]ethyne
(DD-Br) and 5,15-bis[[5', 10',20'-bis[3,5-di(3,3-dimethyl-1-
butyloxy)phenyl]porphinato)zinc(II)]ethynyl]-10,20-bis[3,5-di(9-methoxy-1,4,7-
trioxanonyl)phenyl]porphinato)zinc(II) (DDD). Compound 5 (0.692 g, 5.19 x 10-4
mol),
Pd(PPh3)4 (0.046 g, 3.98 x 10-5 mol), and CuI (0.023 8,1.21 x 10-4 mol) were
added to a 100
mL Schlenk tube. Following the addition of 40 ml of dry THF, a solution of 14
(0.307 g, 3.23
x 10-4 mol) and diethylamine (0.60 ml, 5.80 x 10-3 mol) in 30 ml of dry THF
was added via
canula. The reaction mixture was stirred under N2 at 55 ~C for 65 h, after
which time it was
quenched with water. The organic layer was extracted with CHCl3, washed with
water,
dried over CaCl2, and evaporated. The residue was chromatographed on silica
gel using 1:1
hexanes:THF as the eluent. Two products were recovered: DD-Br 0.318 g (45%,
based on
0.307 g of 14) and DDD 0.193 g (24%). DD-Br:1H NMR (250 MHz, CDC13): 810.49
(d, 2H, J
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= 4.6 Hz, ~3 H),10.39 (d, 2H, J = 4.7 H, /~H),10.20 (s,1H, meso-H), 9.67 (d,
2H, j = 4.8 Hz, ~3
H), 9.36 (d, 2H, j = 4.4 Hz, /~H), 9.35 (d, 2H, J = 4.4 Hz, ~3-H), 9.17 (d,
2H, J = 4.5 Hz, (3-H),
9.17 (d, 2H, J = 4.6 Hz, ~H), 8.99 (d, 2H, J = 4.7 Hz, ~H), 7.51 (d, 4H, J =
2.1 Hz, o-Ph-H),
7.45 (d, 4H, J = 2.2 Hz, o-Ph-H), 6.91 (t, 2H, J = 2.0 Hz, p-Ph-H), 6.88 (t,
2H, J = 2.7 Hz, p-Ph-
H), 4.30 (m, 8H, -O-CH2-C), 4.20 (t, 8H, J = 7.4 Hz, -O-CH2-C), 3.83 (m, 8H, -
O-CH2-C), 3.61
(m, SH, -O-CH2-C), 3.44 (m, 8H, -O-CH2-C), 3.07 (m, 8H, -O-CH2-C), 2.82 (m,
8H, -O-CH2-
C), 2.65 (s,12H, -OCH3),1.84 (t, 8H, J = 7.3 Hz, -OC-CH2-C), 0.99 (s, 36H, -C-
CH3). Vis
(CH2C12): 7~max 410, 429, 441, 479, 546, 686 nm. MALDI-TOF MS m/z : 2198.1
(M+) (calcd
2196.80). DDD:1H NMR (250 MHz, CDC13): 810.53 (d, 4H, J = 4.6 Hz, /~H),10.41
(d, 4H, J
= 4.5 H, ~ H),10.18 (s, 2H, meso-H), 9.37 (d, 4H, j = 4.7 Hz, ,l3 H), 9.35 (d,
4H, j = 5.6 Hz, R
H), 9.20 (d, 4H, J = 4.6 Hz, /fH), 9.16 (d, 4H, J = 4.5 Hz, ~H), 7.57 (d, 4H,
J = 2.0 Hz, o-Ph-H),
7.44 (d, 8H, j = 2.1 Hz, o-Ph-H), 6.84 (t, 6H, J = 2.1 Hz, p-Ph-H), 4.23 (m,
SH, -O-CH2-C), 4.17
(t,16H, J = 7.4 Hz, -O-CH2-C), 3.74 (m, 8H, -O-CH2-C), 3.50 (m, 8H, -O-CH2-C),
3.33 (m, 8H,
-O-CH2-C), 2.99 (m, 8H, -O-CH2-C), 2.78 (m, 8H, -O-CH2-C), 2.61 (s,12H, -O-
CH3),1.81 (t,
16H, J = 7.4 Hz, -OC-CH2-C), 0.97 (s, 72H, -C-CH3). Vis (CH2C12): 7~max (log
s) 410 (5.33),
490 (5.54), 542 (4.34), 563 (4.39), 742 (4.99) nm. MALDI-TOF MS m/z : 3066.6
(M+) (calcd
3065.33).
5,15-Bis[[15"; (5', 10',20'-bis[3,5-bis(3,3-dimethyl-1-
butyloxy)phenyl]porphinato)zinc(II)]-[(5", 10",20"-bis[3,5-di(9-methoxy-1,4,7-
trioxanonyl)phenyl]porphinato)zinc(II)]ethyne]ethynyl]-10,20-bis[3,5-di(9-
methoxy-1,4,7-
trioxanonyl)phenyl]porphinato)zinc(II) (DDDDD). DD-Br (0.259 8,1.18 x 10-4
mol), 7
(0.082 g, 6.71 x 10-5 mol), and diethylamine (0.20 m1,1.93 x 10-3 mol) were
added to a 100 ml
Schlenk tube and dissolved in 40 ml of dry THF. Following the addition of
Pd(PPh3)4
(0.012 8,1.04 x 10-5 mol) and CuI (0.006 g, 3.2 x 10-5 mol) in a dry box, the
solution was
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degassed by three freeze-pump-thaw cycles. The reaction solution was stirred
under N2 at
50 C7C for 84 h. The reaction was then quenched with water; the organic layer
was extracted
with CHC13, washed with water, and dried over CaCl2. Following evaporation of
volatiles,
the residue was chromatographed on silica gel using 30:1 CHCI3:MeOH as the
eluent. The
product mixture was separated by preparative size exclusion chromatography
(BioRad Bio-
Beads SX-1 packed in THF, gravity flow), after which the product pentamer was
re-
chromatographed on silica gel using 20:1 CHCI3:MeOH as the eluent. Yield =
0.163 g (51 %,
based on 0.259 g of DD-Br). 1H NMR (500 MHz, CDC13): b 10.51 (d, 4H, J = 4.6
Hz, ,(~H),
10.47 (m, SH, ~H),10.40 (d, 4H, J = 4.5 Hz, ~3-H),10.15 (s, 2H, meso-H), 9.34
(d, 4H, J = 4.6
Hz, ~H), 9.31 (d, 4H, J = 4.6 Hz, ,(~H), 9.26 (d, 4H, J = 4.5 Hz, /~-H), 9.22
(d, 4H, J = 4.1 Hz, ~
H), 9.17 (d, 4H, J = 4.5 Hz, /~H), 9.12 (d, 4H, J = 4.5 Hz, ,Q H), 7.51 (br s,
8H, o-Ph-H), 7.47 (br
s, 4H, o-Ph-H), 7.40 (br s, 8H, o-Ph-H), 6.76 (br s, 4H, p-Ph-H), 6.66 (br s,
4H, p-Ph-H), 6.50
(br s, 2H, p-Ph-H), 4.12 (t,16H, J = 6.7 Hz, -O-CH2-C), 4.04 (br s,16H, -O-CH2-
C), 3.91 (br s,
8H, -O-CH2-C), 3.52 (br s,16H, -O-CH2-C), 3.41 (br s, 8H, -O-CH2-C), 3.31 (br
s,16H, -O-
CH2-C), 3.22 (br s, SH, -O-CH2-C), 3.15 (br s,16H, -O-CH2-C), 3.08 (br s, 8H, -
O-CH2-C),
2.90 (br s,16H, -O-CH2-C), 2.86 (br s, 8H, -O-CH2-C), 2.72 (br s, 24H, -O-CH2-
C), 2.58 (s,
36H, -OCH3),1.76 (t,16H, J = 7.2 Hz, -OC-CH2-C), 0.93 (s, 72H, -C-CH3). Vis
(CH2C12):
Amax (log E) 412 (5.45), 490 (5.68), 809 (5.27) nm. MALDI-TOF MS m/z : 5454.6
(M+) (calcd
5454.21).
5,15-Bis(trimethylsilylethynyl)-10,20-bis(heptafluoropropyl)porphyrin (15).
Meso-
heptafluoropropyldipyrrylmethane (2.131 g, 6.78 x 10-3 mol) and
trimethylsilylpropynal
(0.856 g, 6.78 x 10-3 mol) were dissolved in 500 ml of dry CH2Cl2. The
solution was
degassed with N2 for 20 min and cooled to -5 ~C. BFg~Et20 (0.17 m1,1.34 x 10-3
mol) was
added via syringe and the reaction mixture stirred for 2 h. The solution was
then warmed
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to room temperature and stirred for an additional 11 h, following which DDQ
(2.30 8,1.01 x
10-2 mol) was added. After stirring for 1 h, the solvent was evaporated and
the residue
chromatographed on silica gel using 3:1 hexanes:CHCl3 as the eluent. Yield =
0.314 g (11 %,
based on 2.131 g of meso-heptafluoropropyldipyrrylmethane). 1H NMR (250 MHz,
CDC13):
b 9.82 (d, 4H, J = 5.1 Hz, ~3 H), 9.46 (br s, 4H, ,(~H), 0.65 (s,18H, -Si-
CH3), -2.08 (s, 4H, N-H).
19F NMR (188 MHz, CDC13): 8 -79.6 (t, 6F), -83.9 (m, 4F), -120.8 (s, 4F). Vis
(CH2Cl2): 7~max
435, 533, 567, 618, 678 nm. ESI MS m/z : 839.1719 [(M+H)+] (calcd 839.1707).
[5,15-Bis(trimethylsilylethynyl)-10,20-
bis(heptafluoropropyl)porphinato]zinc(II)
(16). Compound 15 (0.496 g, 5.91 x 10-4 mol) was dissolved in 100 ml of CHC13
and
refluxed. Zinc acetate dihydrate (0.260 8,1.18 x 10-3 mol) in 15 ml of
methanol was
gradually added; the solution was refluxed for 2.5 h, and subsequently cooled
and
evaporated. The residue was chromatographed on silica gel using 15:1
hexanes:THF as the
eluent. Yield = 0.506 g (95%, based on 0.496 g of the porphyrin starting
material). 1H NMR
(250 MHz, CDCl3): 8 9.77 (d, 4H, J = 5.0 Hz, /j-H), 9.53 (br s, 4H, ~H), 0.65
(s,18H, -Si-CH3).
19F NMR (188 MHz, CDCl3): 8 -79.4 (s, 4F), -79.7 (m, 6F), -120.0 (s, 4F). Vis
(THF): 7~max
(log E) 442 (5.71), 570 (4.05), 591 (4.15), 635 (3.39) nm. ESI MS m/z :
900.0769 (M+) (calcd
900.0764).
[5,15-Diethynyl-10,20-bis(heptafluoropropyl)porphinato]zinc(II) (1~.
Tetrabutylammonium fluoride (1 M in THF,1.12 m1,1.12 x 10-3 mol) was added to
a
solution of 16 (0.455 g, 5.04 x 10'4 mol) in 50 ml of dry THF under N2. The
reaction mixture
was stirred for 10 min, quenched with water, and extracted with CHC13,
following which it
was washed with water, dried over CaCl2, and evaporated. The residue was
chromatographed on silica gel using 15:1 hexanes:THF as the eluent. Yield =
0.377 g (99%,
59
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WO 02/104072 PCT/US02/05584
based on 0.455 g of the porphyrin starting material). 1H NMR (250 MHz,1 drop
pyridine-d5
in CDC13): 8 9.81 (d, 4H, J = 4.9 Hz, /3-H), 9.58 (br s, 4H, ~H), 4.20 (s, 2H,
-CC-H). 19F NMR
(188 MHz,1 drop pyridine-d5 in CDC13): 8 -78.8 (s, 4F), -79.7 (s, 6F), -119.8
(s, 4F). Vis
(THF): ~,max 435, 564, 582 nm. ESI MS m/2 : 790.9659 [(M+Cl)+] (calcd
790.9662).
[(5, 10,20-bis[3,5-bis(3,3-dimethyl-1-butyloxy)phenyl]porphinato)zinc(II)]-
[(5',-15'-
ethynyl-10',20'-bis[10,20-bis(heptafluoropropyl)porphinato)zinc(II)]ethyne (DA-
ethyne)
and 5,15-bis[[5',10',20'-bis[3,5-di(3,3-dimethyl-1-
butyloxy)phenyl]porphinato)zinc(II)]ethynyl]--10,20-
bis(heptafluoropropyl)porphinato]zinc(II) (DAD). Compounds 12 (0.120 8,1.19 x
10-4
mol) and 17 (0.108 8,1.43 x 10-4 mol), THF (30 ml) and triethylamine (3.0 mL)
were added to
a 100 mL Schlenk tube. Following the addition of Pd2(dba)3 (16.3 m8,1.78 x 10-
5 mol) and
AsPh3 (43.7 m8,1.43 x 10-4 mol) in a dry box, the solution was degassed via
three freeze-
pump-thaw cycles. The reaction mixture was stirred under N2 at 35 ~C for 7 h,
and
evaporated. The residue was chromatographed on silica gel using 10:1
hexanes:THF as the
eluent. The recovered bis- and tris[porphinato]zinc(II) products were further
purified by
preparative size exclusion chromatography (BioRad Bio-Beads SX-1 packed in
THF, gravity
flow), followed by an additional round of silica gel chromatography that
utilized 8:1
hexanes:THF as the eluent. Two products were recovered: DA-ethyne 0.100 g
(50%, based
on 0.120 g of 12) and DAD 0.0318 (20%). DA-ethyne:1H NMR (250 MHz,1 drop
pyridine-
d5 in CDC13): 810.56 (d, 2H, J = 4.9 Hz, ~H),10.42 (d, 2H, J = 4.6 Hz, /3
H),10.15 (s,1H,
meso-H), 9.82 (d, 2H, J = 4.9 Hz, ~H), 9.73 (br s, 2H, ~H), 9.60 (br s, 2H, ~
H), 9.35 (d, 2H, J
= 4.6 Hz, ~3-H), 9.31 (d, 2H, J = 4.5 Hz, /~H), 9.13 (d, 2H, J = 4.5 Hz, ~3
H), 7.48 (d, 4H, J = 2.2
Hz, o-Ph-H), 6.94 (t, 2H, J = 2.2 Hz, p-Ph-H), 4.26 (t, 8H, J = 7.4 Hz, -O-CH2-
C), 4.22 (s,1H, -
CC-H),1.89 (t, 8H, J = 7.4 Hz, -OC-CH2-C),1.03 (s, 36H, -C-CH3). 19F NMR (188
MHz,1
CA 02439060 2003-08-21
WO 02/104072 PCT/US02/05584
drop pyridine-d5 in CDC13): 8 -78.9 (s, 4F), -79.6 (t, 6F), -119.8 (s, 4F).
Vis (THF): ~,max (log
s) 429 (5.06), 450 (4.92), 471 (4.96), 484 (4.95), 550 (4.25), 593 (4.14), 688
(4.55) run. MALDI-
TOF MS m/z : 1678.64 (M+) (calcd 1678.44). DAD:1H NMR (250 MHz,1 drop pyridine-
d5 in
CDCl3): 810.56 (d, 4H, J = 5.0 Hz, ,(~H),10.45 (d, 4H, J = 4.7 Hz, ,a H),10.15
(s, 2H, meso-H),
9.76 (br s, 4H, ~fH), 9.36 (d, 4H, J = 4.5 Hz, ~fH), 9.32 (d, 4H, J = 4.4 Hz,
~3 H), 9.14 (d, 4H, j =
4.4 Hz, ,li H), 7.49 (d, 8H, j = 2.2 Hz, o-Ph-H), 6.94 (t, 4H, J = 2.1 Hz, p-
Ph-H), 4.27 (t,16H, J =
7.4 Hz, -O-CH2-C),1.90 (t,16H, J = 7.4 Hz, -OC-CH2-C),1.04 (s, 72H, -C-CH3).
19F NMR
(188 MHz,1 drop pyridine-d5 in CDCl3): 8 -78.9 (s, 4F), -79.6 (s, 6F), -119.7
(s, 4F). Vis
(THF): 7~,max (log s) 432 (5.29), 506 (5.18), 566 (4.49), 593 (4.42), 735
(4.93) nm. MALDI-TOF
MS : m/z 2602 (calcd 2600.87).
5,15-Bis[[15"; (5', 10',20'-bis[3,5-bis(3,3-dimethyl-1-
butyloxy)phenyl]porphinato)zinc(II)]-[(5"; (10",20"-
bis(heptafluoropropyl)porphinato)zinc(II)]ethyne]ethynyl]-10,20-bis[3,5-di(9-
methoxy-
1,4,7-trioxanonyl)phenyl]porphinato)zinc(II) (DADAD). DA-ethyne (0.085 g, 5.05
x 10'5
mol), 5 (0.0344 g, 2.58 x 10-5 mol), dry THF (20 ml), and triethylamine (2.0
mL) were added
to a 50 ml Schlenk tube. Following the addition of Pd2(dba)3 (3.6 mg, 3.93 x
10-6 mol) and
AsPh3 (9.7 mg, 3.17 x 10-5 mol) in a dry box, the solution was degassed via
three freeze-
pump-thaw cycles. The reaction mixture was stirred under N2 at 40 lJC for 18
h, and
evaporated. The residue was chromatographed on silica gel using 1:1
hexanes:THF as the
eluent. The recovered high molecular weight porphyrinic products were
separated using
preparative size exclusion chromatography (BioRad Bio-Beads SX-1 packed in
THF, gravity
flow); the isolated product band was subjected to an additional round of
silica gel
chromatography that utilized 25:1 CH2C12:MeOH as the eluent. Yield = 0.027 g
(24%, based
on 0.085 g of DA-ethyne). 1H NMR (250 MHz,1 drop pyridine-d5 in CDCl3): 810.58
(d, 8H,
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WO 02/104072 PCT/US02/05584
j = 4.8 Hz, ~-H),10.46 (d, 4H, J = 4.3 Hz, ~H),10.40 (d, 4H, J = 4.8 Hz, R-
H),10.16 (s, 2H,
meso-H), 9.80 (br s, 8H, ~3-H), 9.37 (d, 4H, J = 4.3 Hz, ~fH), 9.33 (d, 4H, J
= 4.4 Hz, ~ H), 9.29
(d, 4H, J = 4.4 Hz, ~H), 9.15 (d, 4H, J = 4.6 Hz, ~H), 7.62 (d, 4H, J = 2.2
Hz, o-Ph-H), 7.50 (d,
8H, J = 2.2 Hz, o-Ph-H), 7.06 (t, 2H, J = 2.2 Hz, p-Ph-H), 6.95 (t, 4H, J =
2.2 Hz, p-Ph-H), 4.46
(m, 8H, -O-CH2-C), 4.28 (t,16H, J = 7.3 Hz, -O-CH2-C), 4.05 (m, 8H, -O-CH2-C),
3.87 (m, 8H,
-O-CH2-C), 3.77 (m, 8H, -O-CH2-C), 3.70 (m, 8H, -O-CH2-C), 3.55 (m, 8H, -O-CH2-
C), 3.34
(s,12H, -OCH3),1.91 (t,16H, J = 7.3 Hz, -OC-CH2-C),1.05 (s, 72H, -C-CH3). 19F
NMR (188
MHz,1 drop pyridine-d5 in CDC13): f7 -79.0 (s, 8F), -79.6 (t,12F), -119.7 (s,
8F). Vis (THF):
Amax (log E) 430 (5.35), 507 (5.41), 595 (4.54), 798 (5.25) run. MALDI-TOF MS
m/z : 4525.51
(M+) (calcd 4525.29).
Those skilled in the art will appreciate that numerous changes and
modifications may
be made to the preferred embodiments of the invention and that such changes
and
modifications may be made without departing from the spirit of the invention.
For example,
it is believed that the methods of the present invention can be practiced
using porphyrin-
related compounds such as chlorins, phorbins, bacteriochlorins,
porphyrinogens, sapphyrins,
texaphrins, and pthalocyanines in place of porphyrins. It is also believed
that, in addition to
ethyne and butadiyne moities, the invention can be practiced using other
moieties, including
ethene, polyines, phenylene, thiophene, anene, or allene.
It is therefore intended that the appended claims cover all such equivalent
variations
as fall within the true spirit and scope of the invention.
62
