Note: Descriptions are shown in the official language in which they were submitted.
CA 02231706 1998-03-OS
SUPRAMOLECULAR LAMINATES
Field of the Invention
Thf; present invention is directed to a novel class of synthetic compounds
:5 and more particularly, the present invention is directed to polymeric
supramolecular laminate compounds based on organic or metal-organic materials,
methods of making such compounds and uses of such compounds.
Background of the Invention
1 n Crystal engineering is a field in which new generations of functional
organized molecular assemblies may be rationally developed in the solid state.
Such assemblies may include lamellar, bilayer and monolayer architectures for
applications in membranes, meso gens, surfactants and Langmuir-Blodgett (LB)
films ( 1 ). It is only from an understanding of the crystalline structural
details of
15 such systems that their relationship to specific chemical processes and
functions
may be ellucidated. Crystal engineering of molecular assemblies also provides
a
degree of ~;,ontrol over bulk properties that is not inherently present in
naturally
occurring compounds.
A property of solids that has attracted considerable attention from chemists
20 and crystal engineers is the ability of a solid to adsorb and/or desorb
molecules in
between the two-dimensional sheets in the crystal structure of the solid. Such
molecules are commonly referred to as "guest" molecules and the structure into
which they may be adsorbed or dcaorbe~l is commonly referred to as the "host"
Clays, via intercalation between two-dimensional (2D) layers, and zeolites,
which
25 contain channels and cavities because of rigid three-dimensional (3D)
frameworks,
are natural solid prototypes of considerable commercial interest because of
their
widespread applications in separations and catalysis (5). Some examples of
metal-
organic (6, 7) and organic (8, 9) :~eolite mimics capable of incorporating
organic
CA 02231706 1998-03-OS
guests as well as some examples of "organic clay mimics" capable of exchanging
metal canons have been developed.
U.S. Patents 4,310,440, 4,440,871 and 4,500,651 describe zeolite-type
aluminosilicate and phosphate compounds and their metal substituted
derivatives.
These compounds are used in industrial processes such as ion-exchange,
separation
and catalysis. However, these zeolite-type silicates are not suitable or
adaptable
for other uses because they cannot be controlled with respect to the shape,
size and
function of their pores or the type of molecules they can interact with.
Metal-organic solids presently known and used are either one dimensional, two
dimensional or three dimensional dense solids having no porosity, or solids
made
by linkage, between metals and bi-, tri- or tetra- organic ligands about a
templating
agent which acts to occupy the pores in the crystalline solid. U.S. Patent
5,648,508
discloses such synthetic crystalline metal-organic solids having a microporous
structure. However, these three dimensional frameworks are rigid structures
exhibiting no flexibility and involve covalent bonding within the molecules.
As
such, these structures are not useful for a variety of applications.
Summary of the Invention
The present invention is a synthetic approach using crystal engineering to
produce a new class of compounds which self assemble into polymers having a
laminated structure and which are' structurally related to clays but are
inherently
hydrophobic because of their chemical nature. The compounds are made using
crystal engineering technology to produce both metal-organic and organic
zeolite/cla.y mimics.
The novel compounds of fhe present invention are inert, easy to make and
flexible. 'they are capable of absorbing and desorbing several different types
of
guest molecules and as such are superior to any known types of solid or rigid
synthetic crystalline structures. L>ue to the flexible structure of these
novel
compounds they are suitable for ~;everal varieties of applications as compared
to
2
CA 02231706 2002-10-07
-3-
synthetic compounds having solid, rigid structures. In addition, the three
dimensional molecular- arrangement of the novel compounds of the present
invention are predictable with reasonable accuracy which allows for the
selection
of the type of guest molecule that can bind within the compound. Furthermore,
'_> the compounds of the present invention are relatively easy and cost
efficient to
make and are reusuable.
In accordance with an aspect of the present invention are a synthetic,
supramolecular laminate class of organic compounds having a polymeric two
dimensional flexible architecture comprising organic and metal-organic clay
materials of first row transition metals, wherein the compounds comprise
repeating asymmetric units which self=assemble into laminated three-
dimensional
structures that are expandable with the reversible incorporation of a
hydrophobic
guest molecule within the compound.
In accordance with another aspect of the present izmention is a synthetic
1 '_. hydrophobic clay compound comprising repeating asymetric units having
the
formula: [[NRZ.HZ]X[X]y]~ wherein; X is a polycarboxylic acid; R is a
substituent
selected from the group consisting of hydrogen, an <zlkyl group having 1 to 30
carbon atoms, an aryl group having fr~~m l to 5 phenyl ri~tgs, a benzyl group,
a
phenylethyl group, a phenyl butyl group, an alkylene group, an ethyl ether and
an
2C) alcohol; x and y are present in a ratio of 2:1; and z == 0.
In accordance with another aspect of the present invention is a method for
making a compound having a two-dimensional Ilexible architecture comprising
reacting a solution of amine with a solution of polycarboxylic acid in a
suimblc
CA 02231706 2002-10-07
-~ 3a~-
solvent in a ratio of 2: l by volume; and slowly evaporating the solvent to
obtain
crystals of the compound.
In accordance with yet another aspect of the pres-ent invention is a metal
organic clay compound having the formula: [M(L)z~L')~Xh]" wherein M is a first
S row transition metal; L is a linear bifunctional ligand; L' is a tern~inal
ligand; X
ie r~rnmtarinm a = 1 nr') h ~ ~ 7 nr 2~ anrl n >ll
CA 02231706 2003-07-08
-4-
In accordance with another aspect of the present invention is method of
making a metal organic clay compound, the method comprising forming a
reacting interface between a metal organic solution and a ligand solution
wherein
the reaction product forms in the interface and comes out of solution as
crystals.
Aromatic compounds for use in the crystallization of such metal organic
clay compounds include pure or mixed aromatics which range widely in size and
electronic nature. Examples of such aromatics may be selected from but are not
limited to nitrobenzene, benzene, toluene, xylenes, anisole, veratrole,
naphthalene, methylnaphthalene, and pyrene.
The novel metal-organic and organic salt compounds of the present
invention have widespread applications in the separation of gases, liquids and
solutes. These compounds may also be used as catalysts. Furthermore, these
compounds are ideal as general absorbents/desorbents for aromatics. The
compounds also have environmental applications for example in agriculture for
crop remediation and for pollution clean up of toxic materials from the air
and
water. They also have use as photonic, conducting, non linear optic and
magnetic
materials. Due to the inert and chemically unreactive nature of the compounds
they also have pharmaceutical use for example in the delivery of drugs in vivo
as
well as for use in certain foods as binders for food additives. Finally, these
compounds may also be used to bind explosives such as nitroglycerin or TNT.
According to aspects of the invention the guest molecules for use with the
compounds of the invention may be selected from the group consisting of
nitrobenzene, anisole, veratrole, 1,4-dimethoxybenzene, 1,3,5-trimethoxy-
benzene, m-xylene, mesitylene, p-nitroaniline, tetramethylene,
pentamethylbenzene, hexamethylbenzene, dibenzylamine, naphthalene, 1-
methylnaphthalene, pyrene, tetracyanoethylene, tetrathiafulvalene, ferrocene,
drugs, food additives, water pollutants, air pollutants, explosives,
fluorescent
molecules, pheromones, phosphorescent molecules or nonlinear optic active
molecules.
CA 02231706 2003-07-08
-4a-
Brief Descriution of the Drawings
A detailed description of the preferred embodiments are provided herein
below with reference to the following drawings in which:
Figure 1 shows a scheme depicting various possible layered structures
that are designed using primary or secondary alkylammonium salts of trimesic
acid.
Figure 2 shows the two dimensional hydrogen bonding network observed
in compounds 1-4: 1, [N,N-dipropylammonium]Z[HTMA]; , [N,N-
dihexylammonium]2[HTMA]; 3, [N,N-dioctylammonium]Z[HTMA]; and 4, [N,N-
15
25
CA 02231706 1998-03-OS
dihexylarnmonium]2 [HTMA] } . Five different hydrogen bonds are marked (shown
as dashed lines, a-e, Table 1). The alkyl substituents of the ammonium cations
are
omitted for clarity. N and 0 atoms are shown as hatched and filled circles,
respectively. The dotted lines are: marked on the sheet to show the
alternating
columns of alkyl subsituents.
Figure 3 shows perspective views of the structures of compounds 1 to 4 (a-
d of table 1): 1, [N,N-dipropylammonium]2[HTMA]; 2, [N,N-
dihexylalnmonium]2[HTMA]; 3, [N,N-dioctylammonium]2[HTMA]; and 4, [N,N-
dihexylarnmonium]2[HTMA] }
Figure 4 shows the interdigitated mixed supramolecular laminate structure
of compound 5: [N,N-dibenzylammonium] [N,N-dipropylammonium] [HTMA].
Layer A contains N,N-dibenzylarnmonium and N,N-dipropylammonium cations.
Layer B contains dibenzylammonium canons only. Methyl alcohol is involved in
the hydrogen bonding in layer B.
Figure 5 shows the hydrogen bond networks in [N(benzyl)2H2]2[HTMA]
(mesitylene guest), benzyl groups are omitted for the sake of clarity;
Figure 6 shows the structure of a supramolecular laminate prepared from a
primary alkylammonium cation, phenethylammonium.
Figure 7 shows the hydrogen bond networks in [N(benzyl)2H2]2[HTMA]
(veratrole guest), benzyl groups are omitted for the sake of clarity;
Figure 8 illustrates three modes of crystal packing in supramolecular
laminates based upon [N(benzyl).2H2]2[HTMA] and [N(benzyl)2H2]2[HTML].
Guest molecules are in space-filling mode: Figure 8(a) shows a flat structure
in
which adjacent layers and guests are identical, [N(benzyl)2H2]2[HTML] ~ 1.5 p-
dimethoxybenzene; Figure 8(b) shows a flat sheet in which guest molecules have
alternating packing modes, [N(benzyl)2H2]2[HTML]~ 1-75nitrobenzene,
triclinic, Figure 8(c) shows a corrugated sheet in which adjacent layers and
guests
are identical, [N(benzyl)2H2]2[H:TMA] ~ veratrole~;
5
CA 02231706 1998-03-OS
Figure 9 shows a second embodiment of the present invention. Shown is a
view of taro stacked grids in the metal organic compound la, [Co(4,4'-
bipyridine)2(N03)2]n. The benzene guest molecules (black) engage in stacking
interactions with the 4,4'-bipy ligands of the square grid networks and with
other
benzene molecules; and
Figure 10 shows perspective and overhead views of the structure of
compound lc, [Co(4,4'-bipyridine)2(N03)2Jn. The square grid is presented in
space-filling mode whereas the guest molecules are presented in cylinder mode.
In l:he drawings, preferred embodiments of the invention are illustrated by
way of example. It is to be expressly understood that the description and
drawings
are only for the purpose of illustration and as an aid to understanding, and
are not
intended ass a definition of the limits of the invention.
Detailed lDescription of the Preferred Embodiments
1 S The present invention provides a novel, synthetic, supramolecular class of
organic compounds having a polymeric two dimensional flexible architecture
expandable with the reversible incorporation of guest molecules. These
compounds comprise both metal-organic and organic materials which are capable
of self assembly into laminated three dimensional structures and have an
affinity
for intercalation with guest molecules without affecting their structure. As
such
they are ideal for a wide variety of applications most notably as general
adsorbents
and desorbents of a myriad of organic compounds and gas molecules.
For the purpose of the present invention, "two-dimensional" refers to flat
sheets containing metal-ligand bands or charge assisted hydrogen bonds in the
first
two directions, whereas "three-dimensional" refers to weak forces in the third
direction present between laminated sheets. The term "flexible" as used herein
means conformationally flexible, that is, there are many possible orientations
of the
host framework. As used herein, "guest molecule" refers to the molecule which
lies in between the two-dimensional laminated sheets of the compound which
6
CA 02231706 1998-03-OS
preferably is an organic molecule. "Intercalation" or "intercalated" as used
in the
present invention refers to placement in between laminated layers of the
compound, whereas "interdigitation" refers to substituents on the host
framework
arranged i.n such a way that the head of one substituent sits beyond the head
of the
group above. This resembles a "zipper formation" and is clearly shown in
Figure
1. Intercalated guest molecules push the layers of the host framework apart.
It is
understood that crystallographic methods and terminology may be used herein
that
is well known to those skilled in the art of supramolecular synthesis and
compound
crystallography.
In a first embodiment of the present invention, there is provided a novel
class of synthetic compounds having a two dimensional hydrogen bonded motif
which forms lamellar crystalline structures due to the presence of strong
hydrogen
bonds between complementary organic cations and anions. These synthetic
lamellar clays are hydrophobic and can be made to have an entire three
dimensional molecular predictable arrangement, with reasonable accuracy, due
to
the hydrosphobic interactions between interdigitated alkyl or aryl groups in
the third
dimension.
The compound comprises repeating asymetric units having the formula:
[[NR2H2][X]]2 wherein: X is a polycarboxylic, acid; R is a substituent
selected
from the group consisting of hydrogen, an alkyl group having 1 to 30 carbon
atoms, an aryl group having from 1 to 5 phenyl rings, a benzyl group, a
phenylethyl group, a phenylbutyl group, an alkylene group, an ethyl ether and
an
alcohol; :~ and y are present in a ratio of 2:1; and z > 0. These synthetic
hydrophobic clay compounds preferably comprise primary or secondary
2.5 ammoniwm salts of polycarboxylic acids.
Polycarboxylic acids are suitable templates for the generation of two
dimensional hydrogen bonded arrays. Suitable polycarboxylic acids for use in
the
present invention are both saturated and unsaturated organic aromatic acids
having
at least three carboxylic groups. Preferred acids for use in the present
invention are
7
CA 02231706 1998-03-OS
trimesic acid (H3TMA, 1,3,5-benzenetricarboxylic acid, herein referred to as
HTMA), trimellitic acid {H3TMh, 1,2,4-benzenetricarboxylic acid, C9H606~
herein referred to as HTML) and naphthalene tricarboxylic acid. All of these
acids
for use in the present invention are inexpensive and thermally and chemically
robust polycarboxylic acids having exodentate functionality in two dimensions
meaning that the active functional groups are arranged outside the outside of
the
molecule .and point away from the center.
The process of the invention used to make the crystalline organic salts is
based on deprotonating salts of polycarboxylic acids such as for example
saturated
or unsaturated aromatic acids having at least three carboxylic groups. These
are
reacted wiith amines to afford salts with flat hydrogen bonded sheet
structures.
These rigid hydrogen bonding patterns are robust and the presence of ammonium
canons in the sheet makes such structures ideal for designing interdigitated
supramole;cular lamellar structures since long chain groups such as for
example
alkyl groups can be substituted at the ammonium moiety. For example,
[NR2H2],>[HTMA] and [NR2H2),[HTML]2 are synthesized in a simple processes
by the app>ropriate acid-base reaction in a solvent such as methyl alcohol,
ethyl
alcohol or water. These compounds exhibit their resultant laminate structures
because of the complementary nature of the strong hydrogen bond donors of the
cations and the strong hydrogen bond acceptors of the anions. When R = propyl,
hexyl, octyl or decyl groups, the resultant laminates poorly incorporate guest
molecules. However, it is now demonstrated that when R = benzyl, for example,
interdigita~tion is eschewed in favour of incorporation of solvent or aromatic
guest
molecules.
X-ray crystallographic characterization of several host-guest complexes
based upon [N(benzyl)2H2]2[HTMA] or [N(benzyl)2H2]2[HTML] hosts revealed
that aromatics as divergent in size: and electronic character as nitrobenzene,
anisole, veratrole, 1,4,dimethoxybenzene, 1,3,S,trimethoxybenzene, m-xylene,
mesitylen~e, tetramethylbenzene, pentamethylbenzene, hexamethylbenzene,
8
CA 02231706 1998-03-OS
dibenzylamine, naphthalene, 1-methylnaphthalene and pyrene can be incorporated
as guests by intercalation. It is understood by those skilled in the art that
guests
suitable for intercalation into the compounds of the present invention are not
limited to the guest molecules listed herein, but may also include other guest
molecules selected for specific applications of the compounds. For example,
such
suitable guest molecules may include but are not restricted to explosives,
fertilizers.. pheromones and pharmaceutical agents.
Figure 1 depicts various possible layered structures that may be designed
using secondary alkylammonium salts of trimesic acid. The crystal structures
of
compounds 1-4: l, [N,N-dipropylammonium]2[HTMA]; 2, [N,N
dihexylanlmonium]2[HTMA]; 3, [N,N-dioctylammonium]2[HTMA]; and 4, [N,N-
dihexylammonium]2[HTMA] exhibit identical two dimensional hydrogen bonding
networks stabilized by N+-H...O- and O-H... O- hydrogen bonds as shown in
Figure 1. 'Table 1 is a compilation of hydrogen bond lengths of compounds 1-4
and
demonstrates that the relevant hydrogen bond lengths are almost identical in
each
of the compounds.
The ammonium protons in the sheet are engaged in a robust hydrogen
bonding network and are arranged in alternating columns (Figure 1 ). The
hydropholbic alkyl substituents of~the ammonium canons project above and below
the sheet and the space between the protruding columns of alkyl groups
facilitates
interdigitation or close-packing of the adjacent layers (Figure 2). The
geometrical
arrangement of the cations in the layer is critical and controls the stacking
in the
third direction. The interlayer separations of compounds 1-4 are approximately
7.0~,, 10.3., 12.4., 14.6,, respectively, and are directly related to the
alkyl chain
lengths and the interdigitation of the alkyl groups that facilitate close
packing.
There is a recognizable tilt in the octyl and decyl chains of compounds 3 and
4
with respect to the surface of the sheet (77.2 ° , 73.9 ° ),
especially when compared
to that seen for the propyl and hexyl groups in compounds 1 and 2,
respectively
(87.4 ° , 89.0 ° ). The dimensions of the repeating unit of the
plane are
9
CA 02231706 1998-03-OS
approximately 16.9. x 21.6. in all four compounds, but only correspond to unit
cell parameters i.e. the be plane, in compounds 3 and 4.
A mixed cation supramolecular laminate of HTMA with N,N-
dibenyzlammonium and N,N-dipropylammonium has also been synthesized and is
herein refc;rred to as compound 5 (Scheme lb, Figure 1). Compound 5 is a
doubly
deprotonated salt, the asymmetric unit containing four anions, six N,N-
dibenzylammonium cations, two :L~1,N-dipropyl ammonium cations and one
molecule of methyl alcohol. The crystal structure reveals an interdigitated
supramole;cular laminate architecture with alternating layers of different
1 ~0 composition (Figure 3). The hydrogen bonding pattern of layer A, a mixed
canon
supramole:cular laminate, is similar to that present in compounds 1-4 (Figure
1).
However, layer B, which contains dibenzylammonium canons, has a slightly
different hydrogen bonding pattern as the methyl alcohol molecule is also
involved
in the hydrogen bonding scheme. This observation suggests that a wide range of
1 S new supramolecular laminates is now achievable, and that is now possible
to
generate such laminate compounds exhibiting interesting properties such as
liquid
crystallinity and the ability to intercalate guest molecules.
It is demonstrated that the connectivity of the hydrogen bonding networks
that occurs within the laminates of HTMA salts does not change if the guest
20 molecule us different (Figure 5). The hydrogen bond network with the HTML
salts
(Figure 7) is also invariable with the set of HTML salts thus synthesized.
Furthermc>re, the networks in both HTMA and HTML salts are adaptable enough
to permit at least three crystal packing modes: corrugated sheets, flat sheets
with
identical adjacent layers and guest environment; flat sheets with alternating
layers
25 and guest environment. These structures are exemplified in Figures 8A, 8B
and
8C.
In most of the compounds the proportion of guest varies from 16.6% to
26.3% by mass of the compound and is based upon the relative size of the guest
molecule and the packing mode adapted by the laminate compound. The unit cell
CA 02231706 1998-03-OS
lengths in these compounds are based upon multiples of approximately 12A. x
17~.
x 21 ~.. The 12A distance represents the approximate interlayer separation
whereas
17~. x 21~~ represents the dimensions of the repeat unit within the laminate
(Figure
5). An analogy might reasonably be drawn between the new compounds and lipid
bilayers since the former are effectively an infinite stack of hydrophobic
bilayers.
The interactions between guest molecules and the host frameworks are based
upon
a plethora of edge-to-face and face-to-face interactions between various
aromatic
moieties. In the absence of pest molecules or the presence of a very small
number
of guest or solvent molecules interdigitation of benzyl groups occurs and
interplanar separations are reduced to 8-9A.
The results with monoalkylammonium salts are similar to those just
described.. For example, when R2=H, benzyl, H, phenylethyl or phenylbutyl,
structures based upon alternating hydrophobic and hydrophilic layers are
obtained.
An example of such a structure is 8[HTMA]16[H-phenylethylamine]2,1OH20, and
is illustrated in Figure 6. This compound contains an asymmetric unit having
24
organic residues and 10 water molecules and crystallizes in space group P 1.
The
formula of this compound is C328H372058N16 representing a supramolecular
bilayer. Other compounds of the present invention include but are not
restricted to
C21H36~~206~ C33H60N206~ C41H76N206~ C49H92N206 ~ C133H148N8025
and C200H244N16058.
There are two important observations with respect to these supramolecular
compounds. First, the inherent torsional flexibility of the R2 groups such as
benzyl
and the agility of even strong hydrogen bonds to distort are manifested by
generation of a number of cavity and/or channel geometries. The ability of
these
supramolc;cular laminates to form similar crystalline structures with such a
wide
range of guests is therefore rationalized. Second, the guest molecules can be
easily
removed by heat or vacuum to afford a stable amorphous apohost or exchanged by
contact with solvent that is rich in another guest molecule. When combined
with
the low cost, facile supramolecular synthesis, chemical stability and modular
11
CA 02231706 1998-03-OS
nature, these novel organic compounds have several potential applications in
the
context of separations, sensors and general purpose adsorbents/desorbents.
In accordance with a second embodiment of the present invention are
synthetic two dimensional square grid polymers comprising metal-organic
materials. These polymers are analogous with clay minerals in that they
exhibit
intercalation capabilities in the presence of aromatic compounds and are based
upon square planar or octahedral metals and linear spacer ligands. These
compounds are inexpensive, air/moisture stable, and easy to prepare. These
compoundis are also polymeric two dimensional flexible architectures and may
l0 self assemble into laminated structures.
Thf;se metal organic clay compounds have the formula: [M(L)2(L')aXb]n
wherein Nf is a first row transition metal; L is a linear bifunctional ligand;
L' is a
terminal ligand; X is a counterion; a = 1 or 2; b = 1, 2 or 3; and n > 0.
Suitable
metal ions for use in the compound are divalent or trivalent metals having an
1:5 octahedral or square planar metal center. Preferable first row transition
metals are
Co, Ni, Cu and Zn. The linear bifuntional ligands may be selected from 4, 4'-
bipyridine and its extended versions such as bis(4-pyridyl)ethane. Terminal
ligands suitable for use in the compound of the present invention may include
water, ammonia and pyridine. Suitable counterions may include N03, Cl, S04,
20 SiFg and PF6.
Thc;se metal organic clay compounds are crystallized by adlayering metal
organic solutions with a selected ligand solution. The adlayered solutions
create a
reactant interface after a period of time in which the reaction products
(crystals) are
produced .at room temperature. The formed crystals of the compound fall out of
25 solution and are then separated for use in various applications. If the
solutions are
not carefully adlayered then amorphous powdered materials of the same compound
are obtained. Suitable metal organic solutions for use in the method of the
present
invention may include but are not limited to Co(N03)2-6H20 in methyl alcohol
and Ni(NO3)2-6H20 in methyl alcohol. The ligand solution is preferably 4,4'-
12
CA 02231706 1998-03-OS
bipyridine or one its derivatives in a suitable solvent such as an alcohol,
benzene,
chlorobenzene or naphthalene. Preferred metal organic clay compounds of the
present invention are [Co(4,4'-bipyridine)2(N03)2]n and [Ni(4,4'-
bipyridine~)2(N03)2]n ,where n>0.
Crystallization of [Co(4,4'-bipyridine)2(N03)2~n in the presence of guest
molecules such as benzene, chlorobenzene or naphthalene forms the compounds
[Co(4,4'-t>ipyridine)2(N03)2]n -2benzene (la), [Co(4,4'-bipyridine)2(N03)2]n -
2chlorobenzene ( 1 b) and [Co(4,4'-bipyridine)2(N03)2]n -3naphthalene ( 1 c),
respectively. Crystallization of [Ni(4,4'-bipyridine)2(N03)2]n in the presence
of
chlorobenzene or naphthalene guest molecules forms the compounds [Ni(4,4'--
bipyridine:)2(N03)2~n -2chlorobenzene (2b) and [Ni(4,4'-bipyridine)2(N03)2]n -
3naphthalene (2c), respectively. All five compounds were characterized by
single
crystal x-ray crystallography, the results of which indicate that the
respective guest
molecules are complementary with the square grid framework. Figure 9 reveals
how the guest benzene molecules in compound (la) form edge-to-face and face-to-
face interactions with the hydrocarbon portion of the 4,4'-bipyridine moieties
and
between themselves. These interactions are presumably a driving force for the
clathration of the guests and a major mitigating factor against
interpenetration.
It is understood by those skilled in the art that the type of guest molecules
for use with the metal organic clay compound of the present invention is not
limited to benzene, chlorobenzene or naphthalene but may also include for
example nitrobenzene, toluene, xylene, anisole, veratrole, methylnaphthalene,
1,2-
dimethoxybenzene, pyrene and mixtures thereof. Other molecules may also be
used as guest molecules in the metal organic clay compounds and may be
selected
depending on the desired application of the compound. Suitable guest molecules
may be selected from but are not limited to pharmaceutical agents, pheromones,
explosive chemicals and food additives.
13
CA 02231706 1998-03-OS
The five compounds (la,b,c, 2a, b) all crystallize in space group C2/c and
they have two unit cell parameters in common, i.e. approximately 12A x 22A.
However, the crystal packing in (la), (lb) and (2b) is quite different from
that in (lc)
and (2c). In the case of the former compounds, the square grid layer does not
align
with a unit cell face and adjacent layers are slipped in one direction by
approximately 20%, i.e. every sixth layer repeats. In the case of the latter
compounds, the interlayer separation is large enough that layers are almost
eclipsed. These observations suggest that, although the dimensions of the
square
grids are independent of both metal and guest, interlayer attractions are so
weak
that the guest molecules determine the interlayer separation. Indeed, the
interlayer
separations vary from 5.9A to 8.0 A in the compounds reported herein (Table
2).
Intralayer structure is similar in all compounds with M-N and M-O distances
being
within expected ranges. Tables 3 and 4 reveal the features of 19 additional
square
grid polymers based on [M(4,4'-bipyridine)2(N03)2]n, where M is selected from
Co or Ni.
In compounds (Ic) and (2c) a larger amount of a larger guest is held than in
compounds (la), ( 1 b) and (2b). Indeed, for compounds (lc) and (2c) the
proportion
of the crystal that is occupied by guest molecule is 44% by weight and an even
larger percentage by volume. However, as Figure 10 reveals, the third
naphthalene guest molecule sits comfortably inside the square grid.
Naphthalene is
roughly rectangular but the cavity is able to adapt because one pair of
bipyridine
molecules lies flat whereas the other orients vertically. The remaining
naphthalene
molecules form an infinite stack via edge-to-face interactions similar to
those seen
in pure naphthalene (Figure 10).
In terms of guest:host stoichiometry and crystal packing of the square grids
there are three types of compound. Type A compounds are isostructural with one
another. 'they crystallize in space group C2/c with similar cell parameters,
they
have 2:1 ~;uest:host stoichiometry and they have interplanar separations of
approximately 6A. In these compounds the guest molecules form edge-to-face and
14
CA 02231706 1998-03-OS
face-to-face interactions with the hydrocarbon portion of the 4,4'-bipyrimide
moieties and between themselves. The crystal packing of the square grids in
type
A compounds appears to be influenced by C-H...O hydrogen bond interactions
between 4,4'-bipyridine ligands of one square grid and nitrates of the
adjacent
square grid. These interactions occur in all of the compounds that display the
type
A crystal packing. Pairs of nitrate groups adapt an orientation consistent
with 2-
fold or inversion symmetry and can therefore be regarded as being trans- to
one
another. Interplanar separations do not vary significantly within the scope of
type
A compounds as seen in Table 3. The square grids do not align with a unit cell
face and adjacent grids are slipped in one direction by approximately 20%, ie.
every sixth layer repeats.
Type B compounds have a somewhat larger interlayer separation but there
is still C-H...O hydrogen bonding between 4,4'-bipyridine ligands and nitrate
ligands of adjacent grids. The positioning of grids is different and
facilitates the
1.5 inclusion of one guest molecule in the center of each grid and a larger
interlayer
separation (Table 3). The other guest molecules) lie between the grids and
engage
in stacking; interactions with the 4,4'-bipyridine ligands and themselves.
This is
exemplified by compounds ( 1 i) and (2i). Type B compounds differ from type A
compounds in the orientation of the nitrate ligands and the way in which
adjacent
layers stark. Nitrate ligands on adjacent layers form O...H-C hydrogen bonds
with
4,4'-bipyridine ligands on adjacent layers in such a manner that larger
interplanar
separations are facilitated. The nitrate ligands are orientated on the same
side of
the metal in a cis-type arrangement. There is less uniformity in the crystal
packing
in type B compounds.
Thc: crystal packing in type C compounds is also controlled by weak
interactions between adjacent layers and is a hybrid of the type A and type B
compounds. Intralayer structure is similar in all 19 compounds (Tables 3 and
4)
with M-N and M-O distances being withing expected ranges and C-H..O
interactions between nitrate groups and 4,4'-bipyridine ligands. Each of type
A, B
CA 02231706 1998-03-OS
and C compounds contain hydrophobic cavities within the grid. Furthermore,
these cavities are flexible since the bridging ligands have conformational
flexibility
around the M-M vector. The cavities can therefore either be square or
rectangular,
or, if therf; is distortion around the ligand-metal-ligand angle, then the
cavities may
be rhombic.
To summarize, a supramolecular synthetic approach using crystal
engineering has been used to produce a new class of compounds which self
assemble into three dimensional laminated polymers which are structurally
related
to clays but are inherently hydrophobic because of their chemical nature.
These
new compounds include both metal-organic and organic zeolite/clay mimics.
These compounds are inert, easy to make and flexible. They are capable of
absorbing and desorbing several different types of guest molecules and as such
are
superior to any known types of solid or rigid synthetic crystalline
structures. Due
to the flexible structure of these novel compounds they are suitable for
several
varieties of applications. In addition, the molecular arrangements of these
compounds are predictable with reasonable accuracy which allows for the
selection
of the type of guest molecule that can bind- within the compound. It is
understood
that guest molecules for interdigitation or intercalation with the compounds
of the
present invention can vary widely with respect to the type of guest molecule
and its
size. As the compounds can be specifically designed with respect to the
crystal
packing structure and size it is comprehendible that a novel compound within
the
scope of t:he present invention can be designed for almost any type of guest
compound and can be used in a wide variety of applications.
In the case of both organic and metal-organic compounds, guest molecules
can be easily removed by heat and/or vacuum to afford a stable amorphous
apohost
compound or exchanged by contact with solvent that is rich in another guest
molecule. For this reason, these compounds have potential applications in the
context of separations (e.g. as solid filters or membranes for separations of
enantiomers or isomers), sensors (as bulk powders or as films), as general
purpose
16
CA 02231706 1998-03-OS
adsorbents (e.g. for aromatics from aqueous feeds or volatile organics from
polluted air in the context of environmental remediation; stabilization of
unstable
molecules such as fuels and explosives; or as adsorbents for sensors, in
particular
for aromatics) and/or desorbents (e.g. for crop control via controlled release
of
:5 pheromones, for oral drug delivery). These compounds may therefore also be
used
in the conl:ext of heterogeneous catalysis (reagents adsorb, products desorb),
solid-
state synthesis such as photochemistry (reagents are trapped in fixed
orientation,
reaction occurs, pure product desorbs), separations media including chiral
porous
solids (laminate is chiral by nature or because of enantiomeric substituent),
l n materials science applications such as NLO, magnetism and liquid
crystallinity.
For use as a catalyst, the compound can greatly accelerate the rate of
reaction between two or more reactants while itself being unconsumed.
Compounds of the present invention can be designed as a catalyst for specific
reactions as the metal that sustains the polymer could be chosen for its known
1:5 Lewis Acid or redox activity. Reactions for which compounds of the present
invention may be designed for may include but are not limited to the cracking
of
hydrocarbons and related industrial chemical reactions involved in petroleum
refining and synthetic organic chemical manufacturing.
The; structural nature of the organic compounds makes them amenable to the
20 property of liquid crystallinity. Many of the compounds with long chain
alkyl
substituents show multiple phase and/or colour changes before their melting
point.
As a liquid crystal the compounds resemble liquids in certain respects such as
viscosity and crystals in other properties such as light scattering and
reflection. As
such they may change colour in response to atmospheric changes such as in
2:5 temperature when utilized in certain applications. Uses of such liquid
crystals may
be in TV and electronic display tubes, LED displays, electronic drives in
clocks
and calculators, integrated circuit inspection and other devices.
17
CA 02231706 1998-03-OS
The metal organic compounds have the potential to be used for magnetic
applications. The compounds of the present invention may be used as magnetic
separators in which a magnetic field is used to remove particulates from the
compounds. The compounds of the present invention are inherently paramagnetic
if M is a paramagnetic metal moiety and they have preordained connectivity
between adjacent metal centers.
With respect to use of these compounds to desorb/adsorb guest molecules,
this is accomplished at varying rates depending upon the host structure and
the
guest molecule structure. These compounds therefore have the potential to be
used
as they arc: or in combination with a polymer membrane or as films on
surfaces. In
all cases the synthetic laminated compounds are made in the presence of a
suitable
guest which is subsequently removed. The resulting compound then behaves like
a
clay and adsorbs, via intercalation, a wide range of neutral organic guest
which are
not limited by size or electronic structure. The compound can be used to
adsorb
toxic materials from polluted waste streams or air. Alternatively, due to the
inert
and non toxic nature of the present compounds, they can be incorporated with a
guest for slow release in such applications as drug delivery or pheromone
release
both in vivo and in vitro. The laminate compound itself is recyclable as it is
insoluble in water and common organic solvents and thermally stable to at
least
220°C.
The laminate compounds also have use in nonlinear optics by the
incorporation of guest molecules which are highly polarizable such as p-
nitroaniline. For example, many of the organic host frameworks are inherently
polar by nature and they would therefore be expected to induce parallel
disposition
of guest molecules. For use as a conductive or magnetic material, the metal-
organic laminate compounds can be designed to inherently have such properties
as
part of the: host framework or alternatively, organic compounds can be
designed
using guests such as pyrene, tetracyanoethylene and tetrathiafulvalene. The
18
CA 02231706 1998-03-OS
organic laminate compounds can also be used as liquid crystals when designed
with long alkyl chains.
Both classes of compound may be used as precursors for the generation of
new covalently bonded polymeric materials. In many cases, simply heating the
laminates until they chemically react will afford two or three dimensional
covalent
polymers with structures and composition based upon the laminate and its
guests.
Experimental Procedures
Example 1 - Preparation of HTMA Salts
The series of dialkylammonium salts, [N,N-dipropylammonium]2[HTMA],
l, [N,N-dihexylammonium]2[HTMA], 2, [N,N-dioctylammonium]2[HTMA], 3
and [N,Ndidecylammonium]2[HTMA], 4, were synthesized by slow addition of 2
equivalents of the appropriate amine to one equivalent of H3TMA in methyl
alcohol anal, in order to prevent precipitation of non-stoichiometric
products,
refluxing for 2 hours. Quantitative yields of the colorless solids of
compounds 1-4
were obtained by slow evaporation of MEOH. Crystals of compounds 1 and 2-4
suitable for single crystal X-ray crystallography were obtained from 1-butanol
and
MEOH, respectively (1, m.p. >300°C; 2, m.p. 243°C; 3, m.p.
248°C; 4, m.p.
265°C).
Crystal Data for salts of compounds 1-S: (1) C21H36N206~ monoclinic,
P21/c, a+8.734 (3), B=16.951(7), c=17.811(7), f3=103.99(4)°,
V=2558.70(14)A3,
Z=4, D~ 1.07 Mgm-3. 1427 reflections out of 3349 unique reflections with
I>2.Sa were considered, final R-factors Rf=0.083, Rw 0.068
(2) C33H6pN2O6, monoclinic, P21/n, a=11.531(3), b=16.942(2),
c+19.952(6), I3=98.07(3)°, V=3859.2(16)A3, Z=4, D~ 1.00 Mgm-3. 1339
reflections out of 5042 unique reflections with I>2.56 were considered, final
R-
factors R f=0.090, Rw=0.086. The data for 1 and 2 were measured on an Enraf
Nonius CAD-4 diffractometer at 290K using the w scan mode.
19
CA 02231706 1998-03-OS
(3) C41H76N206, monoclinic, P21/c, a=12.4771(7), b=16.8788(9),
c=21.5789( 11 ), !3=91.992( 1 ) ° , V=4541.7(4)A3, Z=4, Dc=1.01 Mgm-3.
4222
reflections out of 6333 unique relections with L3.0a were considered, final R-
factors R f=0.114, Rw 0.1 O 1.
S (4) C49H92N2~6~ monoclinic, P2l/c, a=14.6856(8), b=16.8941(11),
c=21.592(13), !3=97.970(2)°, V=5305.5(6)A3, Z=4, D~ 1.01 Mgm-3. 2064
reflections out of 4291 unique reflections with I>3.Oa were considered, final
R-
factors R f=0.117, Rw=0.115.
(5) C133H148N8~25~ monoclinic, P21, a=16.7901(3), b=16.8905(2),
c=21.9464(2), f3=96.384(1), V=6185.3(4), Z=2, Dc=1.211Mgm-3. 18350
reflections out of 20242 unique reflections with I>4.06 were considered, final
R-
factors R f=0.083, Rw 0.086.
The intensity data for 3-5 were colected on a Siemens SMART/CCD
diffractometer at 173K using the 8 scan mode. The temperature factors for the
terminal C atoms in the alkyl chains of 1-5 are high, probably a manifestation
of
unresolvable disorder, and account for the relatively high R-values. Atomic
coordinates, bond lengths and angles, and thermal parameters have been
deposited
at the Cambridge Crystallographic Data Centre (CCDC).
Modes of Crystal Packing in [N(benzyl)ZH2JZ[HTMA]
and N benzyl) HZIzLHTML1 Compounds
Figure 8 illustrates three modes of crystal packing in supramolecular
laminates based upon [N(benzyl)2H2]2[HTMA] and [N(benzyl)2H2]2[HTML].
Guest molecules are in space-filling mode: Figure 8(a) shows a flat structure
in
which adjacent layers and guests are identical, [N(benzyl)2H2]2[HTML] ~ 1.5 p-
dimethoxybenzene, orthorhombic, space group Aba2, a= 21.414(1), b=17,161 ( 1
), c
= 24.05 1 ( 1 )A, V= 8840.4(9)A3, Z = 8, p = 1.22 Mgm-3, R= 0.086, Rw = 0.113
for
4670 out of 9675 reflections with 1>26(I); Figure 8(b) shows a flat sheet in
which
guest molecules have alternating packing modes, [N(benzyl)2H2]2[HTML]~ 1-
CA 02231706 1998-03-OS
75nitrobenzene, triclinic, space group P-1, a = 17.089(1), b=21.417(1), c
=24.602(2)A, a 106.568(1),1 = 95.664(1), y= 90,405(1) ° , V =
8582.4(9)A3, Z=8, p
= 1.27 Mgm-3, R = 0.084, Rw = 0.2039 for 15223 out of 36581 reflections with
1>26(I); Figure 8(c) shows a corrugated sheet in which adjacent layers and
guests
are identical, [N(benzyl)2H2]2[HTMA] ~ veratrole~ 1/3EtOH, monoclinic, space
group P21/c, a 11. 5765(6), b = 49.905(3), c = 21- 505(1)A, 13=90.929(1)
°, V =
12423(1)A3, Z = 12, p = 1.22 Mgm-3 , R - 0.076, Rw = 0.139 for 11030 out of
21508 reflections with 1>2~(I). Data were collected on a Siemens SMART/CCD
diffractometer at 193K and structures were solved and refined using SHELX/TL;
Example 2 - Synthesis of Metal Organic Compounds
Compound la: A solution of Co(N03),-6H20 (0.14 g, 0.48 mmol) in
MEOH (20m1) was added to a solution of 4,41-bipyridine (0.23 g, 1.5 mmol) in
benzene (20m1). After standing at room temperature overnight, pink crystals of
la
1:5 were obtained (yield: 0.16 g, 0.24 mmol, 51 %). The presence of the
benzene
molecules was confirmed by IR spectroscopy. When removed from the presence
of mother liquor, crystals become opaque and lose crystallinity within
minutes.
Compound 2b: A solution of Ni(N03)2-6H20 (0-14 g, 0.48 mmol) in
MEOH (20 ml) was added to a solution of 4,4'-bipyridine (0.23 g, 1.5 mmol) in
chlorobenzene (20 ml). After standing at room temperature overnight, light
aqua
green crystals of 2b were obtained (yield: 0.28 g, 0.39 mmol, 82%). The
presence
of chlorobenzene in the bulk material was confirmed by IR spectroscopy.
Crystals
exposed to the atmosphere become opaque and lose crystallinity within several
hours. TGA analysis reveals the following: 32% weight loss from 81 °C
to 162°C.
This data suggests loss of 2 moles of chlorobenzene. Above 162°C, there
is further
decomposition. Crystals of lb were obtained in the same manner (yield 0.25g,
730g).
21
CA 02231706 1998-03-OS
Compound 2c: A solution of Ni(N03)2 6H20 (0.14 g, 0.48 mmol) in
MEOH (20m1) was added to a solution of 4,4'-bipyridine (0.23 g, 1.5 mmol) and
naphthalene (0.62 g, 4.8mmo1) in MEOH (20m1). Aqua blue crystals of 2c were
obtained overnight and were collected by filtration (yield: 0.31 g, 0.36 mmol,
75
%). The presence of the guest molecules was confirmed by IR spectroscopy.
Crystals exposed to the atmosphere become opaque within hours. Crystals of 1 c
were obtained in the same manner (yield 0.16g, 39%). TGA analysis of 1 c
revealed the following: 51.71 weight loss between 1000°C and
2100°C, a further
38.8% weight loss between 210°C and 320°C and no further weight
loss up to
450°C. These weight losses and IR spectroscopy suggest that these
changes
correspond to: loss of naphthalene and N02; loss of 4,4'-bipyridine leaving a
residue of Co304. Similar results were obtained for 2c.
Example :3 - X-ra~r~stallo~raphy - Metal Organic Compounds la,b,c, 2a,b
X-ray data for compound la: 0.2 x 0.3 x 0.4 mm pink rectangular crystal,
monoclinic, C2/c with a 21.3256(3), b = 11.5305(1), c = 12.6079(2) A, l3 =
100.
767 (1) °, Z = 4, V = 3045 .64 (7) A3, _- pcalc = 1. 42 Mgm-3, ~. =
0.61 mm-1,
2.0>26>53.0 ° , T = 173K.
X-ray data for lb: 0.1 x 0.15 x 0.4 mm, pink rod shaped crystal, monoclinic,
C2/c with a = 21.8140( 12), b 11.5281 (2), c 12.8767 (7) A, l3= 102.674 ( 10)
° , Z =
4, V - 3159.3 (3) A3, pcalc = 1.52 Mgm-3, p. = 0.76 mm-1, 2.0>26>54.0°,
T
290K.
X-ray data for lc: 0.20 x 0.40 x 0.40 mm, pink parallelpiped crystal,
monoclinic, C2/c with a = 16.1658(20), b = 11.4940(16), c = 22. 855 (4) A, 13
96.
73 (3) ° , Z = 4, V = 4217.4 ( 10) A3, 2.0>26>49.9 ° , T = 290K.
X-ray data for 2b: 0.15 x 0.15 x 0.3 mm, pale blue rod shaped crystal,
monoclinic, C2Ic with a = 21.678(3), b == 11.4111(10), c=12.9139(16) A, !3 =
103.401 (l l) °, Z = 4, V = 3107. 5 (7) A3, pcalc = 1. 54 Mgm-3, ~ =
0.85 mm-1,
2.0>26>49.8 ° , T = 290K.
22
CA 02231706 1998-03-OS
X-ray data for 2c: 0.15 x 0.30 x 0.30 mm, pale blue plate, monoclinic, C2/c
with a = 16.1014(8), b = 11.3812(6), c = 22.6453(11) A, 13 = 97.306(11)A, Z=
4, V
= 4116.1(4) A3, pcalc = 1. 42 Mgm-3, ~ = 0.53 mm-1, 2.0>26>53.0 °, T =
290K.
Data were collected on Siemens SMART CCD (la, lb, 2c)or Enraf Nonius
.'> CAD-4 ( 1 c, 2b) diffractometers with Moka radiation (~, = 0.70930 A)
using the
6/26 or w/26 scan modes, respectively. Structures were solved by direct
methods
and refined using the PC version of the NRCVAX system. Non-hydrogen atoms of
the coordination polymer and guest molecules were refined with anisotropic
thermal parameters. The naphthalene molecules that sit inside the square grid
in lc
and 2c were observed to have significantly higher thermal motion than other
guest
molecules. The following values were obtained: la, R = 0.039, Rw = 0.049, 2613
out of 3177 reflections with I > 4.0 6(I) and 206 parameters; lb, R 0.058, Rw,
_
0.075, 2425 out of 2791 reflections with I > 3.0 6(I) and 215 parameters; lc,
R =
0.054 and Rw = 0.056 were obtained for 2730 out of 3614 reflections with I >
2.5
1.'i ~(I) and 31)5 parameters; 2b, R = 0.054, Rw = 0.056, 2186 out of 2739
reflections
with I > 3.0 6(I) and 215 parameters; 2c, R = 0.078, Rw = 0.109, 3203 out of
4275
reflections with I > 4.0 6(I) and 251 parameters. Hydrogen atoms of the 4,4'-
bipyridine moieties and guest molecules were placed in calculated positions
with
dC_H, = 1.00 A. Residual electron density (min./max., eA-3): -0.88/0.87, -
1.31/1.17, -0.43/0.35, 1.17/1.08 and -0.66/0.60 for la, Ib, lc, 2b and 2c,
respectively.
23
CA 02231706 1998-03-OS
Table 1: Hydrogen Bonding Distances (A) in the 2D Layers of Compounds 1-5
O...O N...O
a b c d a
1 2.540(6) 2.773(8) 2.732(6) 2.887(8) 2.654(8)
2 2.511(10) 2.765(12) 2.728(11) 2.834(12) 2.635(15)
3 2.543(4) 2.772(5) 2.701(4) 2.829(4) 2.654(4)
4 2.524(12) 2.766(13) 2.696(11) 2.818(13) 2.690(13)
5@ 2.567(7) 2.751(8) 2.709(8) 2.809(8) 2.687(7)
2.777(8) 2.769(7)
@Compound 5 crystallizes in a non-centrosymmetric space group (P21 ).
Consequently, unlike compounds 1-4, there is no crystallographic inversion
center
across b and c.
1:~
Table 2: A Comparison Of The Salient Structural Features
Of The Square Grids In Compounds la, lb, lc, 2b And 2c
Compound Guest Cell Vol Interlayer Dimensions of Grid Separation
A3 A
1 a C6H6 3045.6(2) 5.9 11.43 x 11.53094.0
lb C6HSCl 3159.3(3) 6.1 11.479 x 11.52894.1
1 c C 1 OHg 4218(2) 8.04 11.494 x 11.43490.2
2b C6HSC1 3107.5(7) 6.1 11.436 x 11.41193.6
2c ClOHg 4116.1(4) 7.99 11.331 x 11.38190.4
24
CA 02231706 1998-03-OS
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CA 02231706 1998-03-OS
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CA 02231706 1998-03-OS
Although preferred embodiments have been described herein in detail, it
is understood by those skilled in the art that variations may be made thereto
without departing from the scope of the invention as defined by the appended
claims.
27
CA 02231706 1998-03-OS
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