Note: Descriptions are shown in the official language in which they were submitted.
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New inetal-organie frameworks and their use for encapsulation of fluorescent
dyes
Field of the invention
The present invention relates to new microporous metal-organic frameworks
(MOB),
a new host-guest complexes of the said 14,40Fs with dye molecules, as well as
their fluorescent
properties.
Background of the art
Synthesis and application of microporous metal-organic frameworks (,40Fs) is a
field.
of material science which have attracted a lot of attention in recent years.
Compared to tradi-
tional porous materials, like silica or zeolites. MOFs have open channels with
a much wider
variety of pore sizes, volume of internal cavities and nature of pores
surface. Compared to
other types of porous materials MOFs has one of the highest relative surface
areas. Large va-
riety of constituents together with a flexible design makes MOFs a versatile
platform for nu-
merous applications including gas storage or separation, catalysis, sensing,
encapsulation of
active compounds and many others (Cui, Y; Li. B.; He, H.; Zhou, W.; Chen, 13.;
Qian, (3. Ace,
Chem. Res. 2016,49(3), 483-493),
MOEs are coordination network compounds comprised of nodes, which are metal-
containing inorganic groups, connected together with polydentate organic
ligands. Ligand is
connected to nodes through coordinating functional groups, such as
carboxylates and amines.
Together they form one-, two-. or three-dimensional lattices, which often
exhibit crystalline
structure. in many instances they contain pores a.s channels and cavities of
various diameters,
which can contain solvent or other organic molecules. In many instances, if
the size of a mol-
ecule is comparable to the diameter of a channel, such molecules can be
introduced to pores
or extracted from them by diffusion (Cirujano, F. G.; Llabres i Xamena, F. X.
Metal Organic
Frameworks as Nanoreactors and Host Matrices for Encapsulation. In Organic
Nanoreactors;
Elsevier, 2016; pp 305-340).
Encapsulation of small organic molecules in MOFs and formation of host-guest
com-
plexes involves interaction of guests with walls of channels and cavities,
where they are con-
tained. Various modes of interaction between host and guest include sorption,
coordination
and chemical reaction. Understanding of the details of interaction between
host MOE lattice
and guest organic molecules is a prerequisite for the creation of new
composite materials with
useful functions. While coordination and chemical reaction often produce well-
defined host-
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guest complexes, which can be characterized by a number of methods, sorption
is reversible
by nature and produce much weaker host.--guest complexes. In. one aspect it is
advantageous to
use fluorescent molecules as guests and to assess their interaction with hosts
by changing of
their fluorescent properties (Karmakar, A,; Samanta, P.; Desaiõ A. V.; (Thosh,
S. K. Ace,
Chem. Res. 2017, 50(10), 2457-2469).
Sorption of various ions and molecules from solution by porous M(I)Fs is
described in
a number of publications (Gao, Q.; Xu, J.; Bu, X.-H. Coordination Chemistry
Reviews 2019,
378, 17-31), This effect i.s of interest for selective removal of certain
pollutants from water
streams (Oil, Z.; Zhang, X.; Liu, S.; Zhou, L,; Li, W.; Zhang, J. inorg. Chem.
2018, 57(18),
11463-11.473; Guo. 11; Sun, Y.; Zhang, F.; Ma, R.; Wang, F,, Sun, S.; Guo, X.;
Liu, S.;
Thou, T. Inorganic Chemistry Communications 2019, 107, 107492) or for their
degradation
(Li, H.-P.; Dou, Z.; Chen, S.-Q.; Hu, M.; Li, S.; Sun, H.-M.; Jiang, Y.; Zhai,
Q.-G. inorg.
Chem. 2019, 58(16), 1.1.220-11230; Qiao, X.; Ge, Y.; Li, Y.; Niu, Y.; Wu, B.
AC'S Omega
2019, 4(7), 12402-12409). Efficiency of the sorption process is assessed by
measurements of
ultraviolet-visible spectra in solution. However, there is a lack of research
and characteriza-
tion of host-guest complexes, formed when a molecule is adsorbed inside MOF
pores. Espe-
cially interesting it would be to investigate properties of guest molecules,
which have their
own emission spectra. There is no literature data for solid-state fluorescence
measurements of
fluorescent molecules encapsulated in MOF pores.
Detailed description
Disclosed herein are novel metal-organic framework materials having
tetradentate
tetraphenylantbraquinone linking moieties and one or more secondary building
units.
in one embodiment, a secondary building unit comprises metal ions which are
selected
from Cu or Ni, In another embodiment a secondary building unit comprises of
the same metal
ions (Cu or Ni) and atoms of oxygen with 0/metal ratio is >0.5, preferably
>0.6. In one aspect
a schematic representation of Cu-Arith-MOF is illustrated by Fig. 1 In another
aspect a
schematic representation of NI-Arith-MOF is illustrated by Fig. 2.
In one embodiment the present disclosure is directed to preparation of a new
MOF
material, which may comprise of a compound represented by the formula.
(Formula 1):
MõõL,Ay*Bil<nSolv
2
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Formula I.
where M is selected from: Cu, Ni;
L represents tetradentate tetraphenylarithraquinone ligand of formula Li;
HOOC 0 COOH
0
HOOC -COOH
LI
A independently represents a ligand selected from (OH), H20, alkyl-(S03)-,
ary1-(S031,
(N021, halide anion;
B independently represents a ligand selected from OK, 11,0, alkyl-(S03)-, ary1-
(S03)-,
(NO2), halide anion;
SoIv represents any solvent that can coordinate with the moF metal ions. It
may be a solvent,
which participated in MOTH' formation selected from the list: water,
dimethylformamide, di-
ethylformamide , dimethylacetamide, die th ylace tamide dime.thyl s Li ITO
Xide. .
w represents the number of M atoms in the building unit;
x represents the number of ligands L in the building units;
y represents the number of ligands A in the building unit;
z represents the number of ligands B in the building unit;
n represents the average number of solvent molecules "Sole coordinated to the
metal centers
M per -building unit in the MOF material.
Preferably, the ratio ylx is more preferably
Preferably, the ratio zix. is in range and
Ligand LI was synthesized and used as the organic linker as it is described in
Exam-
ples section. There are no literature methods for preparation of ligand of Ll
formula. Accord-
ing to present invention a new and efficient synthetic method was developed
for its prepara-
don, as it is indicated on Scheme 1. A short four-step sequence commence with
a cross-
coupling step, followed by oxidation of sulfur yielding substituted thiophene
1,1-dioxide 4. It
was gratifying to found, that substance 4 is reactive in Diels-Alder
cycloaddition and yields a
corresponding tetrasubstituted anthraduinone 6. For the first time it wa.s
shown, that a thio-
3
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phone 1,1-dioxide substituted at positions 3 and 4 by phenyls with an electron-
withdrawing
group can undergo such transformation. Finally, hydrolysis of esters in 6
provided ligand
In one embodiment Cu(NO3)2-2.511k0 salt was chosen. to provide a metal node
for the
preparation of Cu-Anth-M0F. In another embodiment Ni(NO3)2-6F120 salt was
chosen to
provide a metal node for the preparation of Ni-Anth-M0F.
Experimental conditions for the preparation of Cu-Anth-MOF and Ni-Anth-MOF
were optimized in. such a. way, that single crystals could be formed by the
reaction of a. metal
salt and the organic ligand 1,11. Preferably, the crystal topology shall be
related to a monoclin-
ic crystal system and the P21ic or P2im space group or a sub-group. Cell,
parameters and other
data for Cu-Anth-MOF are represented in Table 1. Cell parameters and other
data for Ni-
Anth-MOF are represented in Table 2. Both Cu-Anth-MOF and Ni-Anth-MOF demon-
strated excellent robustness upon isolation and storage. Together with a
permanent porosity of
the prepared 14,40Fs it makes them ideal candidates for the preparation of
host-guest complex-
es with organic molecules.
In one aspect the process of preparation of Cu-Auth-MOF the solvent, which is
used
for the preparation comprises a mixture of water and an organic solvent in
ratio organic sol-
vent/water from 90:1.0 to 65:35, expressed as a volume % of organic solvent.
Organic solvent
is preferably selected from the list: dimethylformarnide, diethylformamide,
dimethylacetam-
ide, diethylacetamide, dimethylsulfoxide; preferably carboxylic acid
dimethylamide; prc.fc.Ta-
b y dimeth ylform amide.
In another aspect the process of preparation of Ni-.Anth-MOF the solvent,
which is
used for the preparation comprises a mixture of water, an organic solvent 1
and an organic
solvent 2. Content of water in volume is preferred to be less, than 50 1,7on,
preferably less
than 30%. Ratio between organic solvent llorganic solvent 2 is preferred to be
50:50, prefera-
bly- 60:40. Organic solvent 1 is preferably selected from the list: dioxane,
tetrahydrofuran,
preferably dioxane. Organic solvent 2 is preferably selected from the list:
dimethylformamide,
diethylformatnidc., dimethylacetamidc., diethylacetamidc., dimethylsulfoxide;
preferably car-
boxylic acid diethylamide; preferably diethylformamide.
According to the current disclosure; MOFs based on tetraphenylandiraquinone
ligand
of formula Ll can be prepared in a form, where the coordination polymer is
ordered, prefera-
bly in a. single-crystalline form. The structure of MOFs disclosed thereof was
confirmed by
single-crystal X-ray diffraction.
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In one embodiment a spatial arrangement of elements of Cu-Anth-MOF is exempli-
fied by Fig. 3, which demonstrates a. single-crystal X-ray structure of Cu-
Antit-M0F.
in another embodiment a spatial arrangement of elements of Ni-Auth-MOF is exem-
plified by Fig. 4, which demonstrates a single-crystal X-ray structure of Ni-
Anth-M0F.
In another example crystalline nature of the prepared material is confirmed by
powder
X-ray diffraction as exemplified by Fig, 5 for Cu-Anth-MOF,
In yet another example crystalline nature of the prepared material is
confirmed by
powder X-ray diffraction as exemplified by Fig. 6 for Ni-Antit-M0F.
In one embodiment Cu-Arith-MOF and Ni-Anth-MOF are stable in water.
Preferably, the three-dimensional structure of Cu-Anth-MOF incorporates
channels
having an internal diameter between 7.9 and 10.2 A. and are accessible through
apertures with
diameters 7.9 and 10,2 A, Advantageously, the three-dimensional structure of
Ni-Anth-MOF
incorporates channels having an internal diameter between. 6.4 to 8.5 A and
are accessible
through apertures with diameters 6,4 to 8.5 A.
The present invention relates to a guest encapsulated in a host and a method
of encap-
sulation. The host comprises of a MOF and the guest comprise a molecule having
a size
smaller, than the aperture size of the M(I)F. In one embodiment a dye
"Methylene Blue" (MB)
is used as a guest. Molecular representation of MB is shown on Fig. 9, The
size of MB mole-
cule was estimated as a rectangular box of approximate dimensions 17,0 x 7.6 x
3.3 A. Fluo-
rescence of the solution of MB in water at a concentration c,I wriolliL and pH
7 with excita-
tion at 290 nrn is indicated on Fig. 11. This emission spectrum is
characterized by a strong
peak in a range 650-750 Mil with signal intensity higher that 100000 arbitrary
units.
In one aspect MOF materials disclosed herein, in particular Cu-Anth-MO.F or NI-
Anth-MOF was characterized by fluorescence spectroscopy. Spectrum of solid-
state fluores-
cence emission characteristics of Cu-Aitth-MOF is shown on Fig. 12, Spectrum
of solid-state
fluorescence emission characteristics of Ni-Anth-MOF is shown on Fig. 14. Both
spectra are
characterized by very low fluorescence intensity in 650-750 rim range, in
particular, signals in
this range are lower than 500 arbitrary units.
In one embodiment the present invention provides a method for preparing of a
host-
guest complex. Scheme 200 of preparation of host-guest complexes of Cu-Anth-
MOF and
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Ni-Anth-MOF with MB and measurement of its fluorescent properties is outlined
on Fig. 10.
At a step 205 the method can include mixing of a moF with water, At a step 210
a solution of
a guest in the same solvent is prepared. At a step 215 components obtained at
steps 205 and
210 are mixed and incubated without. stit-ring according to example provided
in the current
disclosure.
In one embodiment, when MB is used as a guest and Cu-Anth-MOF is used as a
host
a new host-guest complex can be prepared at step 215. Fluorescence spectrum of
the said.
complex is measured at step 220.
A graph representing solid-state emission characteristics of a host-guest
complex.
comprised of MB encapsulated in Cu-Anth-MOF (excited at 290 nm) is shown on
Fig. 13, A
graph representing solid-state emission characteristics of a host-guest
complex comprised of
MB encapsulated in Ni-Auth-MOF (excited at 290 nin) is shown on Fig. 15 for Ni-
Anth-
IMF. Both Fig. 13 and Fig. 15 demonstrate that fluorescence intensity in range
650-750 rim
is below 2000 arbitrary units which means, that MB confined in pores of Cu-
Anth-MOF or
Ni-Anth-MOF does not exhibit fluorescence. This data demonstrates the unique
property of
the new MOFs described thereof. When a dye molecule is encapsulated inside the
pores of the
said MON, its fluorescence is completely quenched.
At step 225 a digestion of a host-guest complex with encapsulated MB is
carried out
in aq. HC1 solution. Under these conditions a complete decomposition of the
polymeric struc-
ture of a MOP to an initial ligand and a metal salt takes place. MB is
liberated to the solution.
At step 230 the solution after digestion is neutralized to pH 7 and its
fluorescence is measured
directly from the aqueous solution, In one aspect a.s demonstrated on Fig. 16
for Cu-.Anth-
MOF fluorescence of MB is restored after digestion and its emission spectrum
contains a
strong signal in 650-750 mu range with intensity higher than 30000 arbitrary
units. In another
aspect as demonstrated on Fig. 17 for Ni-Antb-MOF fluorescence of MB is
restored after
digestion and its emission spectrum contains a strong signal in 650-750 nm
range with inten-
sity higher than 15000 arbitrary units. The provided data demonstrates that
interactions in the
host-guest complex of the dye molecule inside the pores of the new MOFs quench
dye fluo-
rescence with an excellent etticiency. .At the same time, the said
interactions are reversible
and once the dye is extracted from the pores its fluorescence is restored.
Examples
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All reagents were obtained from commercial sources and used without further
purifi-
cation. The emission fluorescent spectra were recorded, at room. temperature,
using Edinburgh
Instruments .FS5 Spectrofluorometer.
Scheme I demonstrates the reaction pathway for the preparation of ligand of
formula
Ll from starting materials. First, 3,4-dibromothiophene I_ was arylated by
boronic acid 2 in a
Suznki-Miyaura cross-coupling reaction. Obtained diaryithiophene 3 was
oxidized by Ox-
one to the appropriate thiophene 1,1-dioxide 4. Double Die's-Alder reaction
between thio-
phene 1,1-dioxide 4 and 1.4-benzoquinone 5 furnished tetrasubstituted
andiraquinone 6. Fi-
nally, hydrolysis of ethyl ester groups in 6 yields the target ligand Ll.
COOEt EtO0C
Br\ Br
(H0)2B = 2 Oxone, NaHCO3
S __________________________________________________________________
Na2CO3, PPh3, Pd(OAc)2 DCM, acetone, H20
toluene water (2:1), rt, 48 h
1 110 `C, 48h 3
EtO0C
EtO0C C)
0
lel 5
0
S :
0 AcOH, sealed tube, EtO0C 0
COOEt
120 `C, 100 h
4 0
EtO0C EtO0C 6
COOEt
HOOC COOH
0
KOH, Et0H
100 `C, 24 h
0
HOOC Ll COOH
Scheme 1
Abbreviations
AcOH Acetic acid
CDCI3 Chloroform-d
Cu(NO3)2.2.5H20 Cupric nitrate hemi(peTitahydrate)
DCM Dichioromethane
DEF NeN'-Dietl-pylformarnide
DIMS0 Dimethyl.sulfoxide
Et0Ac Ethyl acetate
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Et01-1 Ethanol
HCi Hydrochloric acid
KOH Potassium hydroxide
Na2CO3 Sodium carbonate
NalS203 Sodium thiosulfate
NatIC03 Sodium bicarbonate
Ni( NO3)2 6H20 .Nickel(11) nitrate hexahydrate
Pd(OAc)2 Palladium(II) acetate
PPh3 Tripheny 1phosphine
Preparation of diethyl 4,4'-(thiophene-3,4-diAdibenzoate 3. In a 100 ml screw-
cap
vial under argon flow and stirring (4-(ethoxycarbonyl)phe,nyl)boronic acid 2
(7.0 g, 36.21
mmol, 4.0 equiv.), solid Na2CO3 (3.8 g, 36.21 mmol, 4.0 equiv.), Pd(OAc)? (0.2
g, 0.91
mmol, 10 mol%) and PPh3 (0.6 g, 2.26 mmol, 25 mol.%) were successfully
introduced, and
followed by 3,4-dibromothiophene 1 (1.0 roL, 2.19 g, 9.05 mmol), and the
mixture was fur-
tiler purged with argon for 15 min at rt. Meanwhile, dry toluene and water
were separately
subjected to degassing sequence by connecting vacuum line and then purging
with argon
through rubber septum. The operation was repeated at least 3 times. Finally,
degassed toluene
(45
and water (1.5 mL) were added into the reaction vessel, which was then
sealed and
heated to 100-110 "C for 24 h. Cooled to rt. The reaction mixture was diluted
with Et0Ac
(100 mL), aq. layer was separated and further washed with Et0Ac (3 x 30 aiL).
The organic
phases were pooled together, washed with water (30 mt.) and brine (50 mi..),
and evaporated
onto 35 g of silica. Crude compound was purified with column flash
chromatography, eluting
with Et0Aelhexanes gradient from 0 to 30%. Yield of 3: 2.5 g (6.6 mmol, 72%),
as a white
solid. 111 NMR (400 MHz, CDC13) 8: 7.94 (d, 2H), 7.41 (s, 21:1), 7.23 (d, 2H),
4.37 (q, 2H),
1.39 (t, 3M = = C l',qN1R (100 MHz, CDC13) 8: 166.6, 140.9, 140.8, 129,7,
129.3, 129.0, 125.5,
61.1, 14.5; GC-MS (PI): mh. 380 [Mr.
Preparation of diethyl 4,4`41,1-dioxidothiophene-3,4-diy1)dibenzoate 4.A
solution of
thiophene diester 3 (5.5 g, 14.5 mmol) in DCM/a.cetoneiwater (2:1:2) solvent
mixture (500
mL total volume) was introduced into a 1000 ml round-bottom flask under ice-
water cooling
and intense stirring. Next, NafiCO3 (59 g, 690 mina 45 equiv.) was added in
one portion fol-
lowed by Oxone (96 g, 146 mmol, 10.0 equiv.) in small portions, 5-7 g each
within 5 h, and.
the reaction mixture was left for overnight at
After that, the mixture was diluted with water
(400 mL), organic layer was separated, aq, layer was further extracted with
DCM (5 x 100
mi..). The organic phases were pooled together, washed with 10% al. solo. of
Na2S203 (2 x 50
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mL), water (50 mt.) and brine (50 mL), and evaporated onto 35 g of silica.
Crude compound.
was purified with column flash chromatography, eluting with Me0H/D.C.N1
gradient from 0 to
5%. Yield of 4: 2.7 g (6,5 mmol, 45%), as a light-yellow foam, which solidify
upon standing.
111 MIR (300 MHz, CDC13) 8: 7,97 (d, 2if), 7.12 (d, 2I1). 6.73 (s, 2H), 4.38
(q, 2H), L39 (t.
31-1) LC-NIS (ES+): adz 413 IM Hl+.
Preparation of tetraethyl 4,4',4",49"-(9,1 -rii()X0 -9,/0-dihydroanthracene-
2,3,6,7-
tetrayl)tetrabenzoate 6. In a 100 ml screw-cap vial under argon flow and
stiffing a solution of
thiophene Li-dioxide 4 (2.0 g, 4,85 mrnol) in glacial Ac011 (25 mt.) was
introduced followed
by 1,4-benzoquinone 5 (0.3 g, 2.78 mmol, 0.5 equiv.). The vessel was then
sealed and heated
to 110-1.20 "C for 48h, After that. the reaction mixture was cooled to it and
poured into water
(250 mL) and extracted with DCM (5 x 50 mL), organic layers were pooled
together, washed
with sat. aq, NaHCO3 (2 x 50 mL), water (50 mL) and brine (50 mL), and
evaporated onto 35
g of silica. Crude compound was purified with column flash chromatography,
eluting with
Et0Adhe.xane.s gradient from 0 to 30%. Yield of 6: 1.2 g (1.5 Immo', 31%) as a
light-yellow
solid, 1H NMR (400 MHz, CDC13) 8: 8.42 (s, 4H), 7,99 (d. 8H), 7.31 (d, 8H),
4.41 (q, 811),
1.42 (t, 12H); 13C I\TMR (100 MHz, CDC13) 5: 182.3, 166,2, 145.7, 143.7,
132.9, 130.1, 129.8,
129.8, 61.3, 14.5.
Preparation of
4,4',4",4"`-(9,10-dioxo-9,10-dihydroanthracene-2,3,6,7-
tetrayl)tetrabenzoic acid Li. In a 25 ml screw-cap vial under stirring a
solution of ester 6 (350
mg, 0,44 mmol) in Et0H (5.0 mi.) was introduced followed by KOH (0.15 g, 2.65
mmol, 6.0
equiv,). The vessel was then sealed and heated to 100-110 "C for 24 h, showing
complete
conversion. The mixture was cooled to rt and poured into water (50 mL) and
acidified with
1N aq, HC1 to pH 3, precipitated solids were filtered, washed with water (5 x
10 mi.), and
dried under reduced pressure to constant weight. Yield of
2.60 mg (O,37 mmol, 84%), as a
-
light-yellow solid. H NMR (400 MHz, DMSO-d6) 6: 13.08 (br.s, 41-), 8.27 (s,
4H), 7.90 (d.
8H), 7.39 (d, 8H); LC-MS (ES--): miz 687 [M---111---,
Synthesis of Cu-Antrh-MOF A mixture of L1 (10 mg. 0.015 mmol) and
Cu(NO3)2-2,5H-20 (14 mg, 0.060 mmol) was dissolved in a mixed solvent of DEF
(1.0 mt)
and water (0.1 mL), Upon the addition of 1) uL. of 6 M aq, FiC1, the vial was
capped and
heated at 90 'C. for 24 h. After cooling to room temperature the green
crystals were formed.
They were collected by filtration and dried at rt. Yield of Cn-Anth-MOF: 8
FrI2 (65%)
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Synthesis of Ni-Anth-MOF. A mixture of Li (17 mg, 0.025 mmo1) and.
Ni(NO3)2-6H70 (22 ma, 0,058 imn61) was dissolved in a mixed solvent of DEF
(1.0 nit:), wa-
ter (0.5 mL) and dioxane (1.5 nit). Upon the addition of 30 ,t1L, of 1 M aq.
HO, the vial was
capped and heated at 100 "C for 4 days. After cooling to room temperature
greenish crystals
were formed. They were collected by filtration and dried at rt. Yield of Ni-
Anth-MOF: 10
mg (51%).
Single-crystal XRD and crystal structure of Cu-Ant/2-1110F SCXRD data of CAI-
Anth-MOF were collected. using Xta.LAB Synergy, Dualflex , HyPix,
diffractometer using Cu
, 1.54178 A) radiation, Data indexing, integration and reduction was performed
using
CrysAlis PRO 1,171,40.35a (Rigaku OD, 2018) software. Absorption correction
was per-
formed by multi-scan method. Structure was solved using Direct Methods (SHELXT
2014/4,
Sheldrick, 2014) and refined using SHELXL201711 (Sheldrick, 2017) (full-matrix
least-
squares on 0. Crystal data and refinement conditions are shown in Table 1. All
attempts to
refine peaks of residual electron density of disordered solvent molecules were
unsuccessful.
Therefore the data were corrected for the contribution of a disordered solvent
density using of
the SQUEEZE procedure as implemented in PLATON. The total solvent accessible
void vol-
ume is 3141 A.
Table 1, Crystal data and structure refinement conditions for Cu-Anth-MOF
Chemical formula C42H24Cu2012
Mr 847.69
Crystal system, space group Monoclinic, P2 dc
Temperature (K) 170
a, b, c (A) 18.7415 (2), 23.1192 (2), 14.4500 (1)
106.064 (1)
V (A3) 6016.55 (10)
4
Radiation type Cu Ka
(mm-I) 1.22
Crystal size (mm) 0.08 x 0.06 x 0.05
Diffractometer XtaLAB Synergy, Dualflex, HyPix
Absorption correction Multi-scan
Tmin, Tmax 0.741, 1.000
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No. of measured, independent and ob- 58543, 12227, 10165
served [I> 2a(/)[ reflections
Rint 0.055
(sin 0/2)õ,ax (A-1) 0.631
R[F2 > 2a(F2)], wR(F2), S 0.059, 0.182, 1.04
No. of reflections 12227
No. of parameters 507
H-atom treatment H-atom parameters constrained
Apma,õ Apmin (e A-3) 0.98, -0.56
Single-crystal XRD and crystal structure of Ni-Antrh-MOF SCXRD data of .Ni-
Anth-
MOF were collected using XtaLAB Synergy, Dualfle,x, HyPix, diffractometer
using Cu Ka (3%.
= L54178 A) radiation. Data. indexing, in teffration. and reduction. wa.s
performed using CrysA-
Us PRO 1.171..40.35a (Rigaku OD, 2018) software. Absorption correction was
performed by
multi-scan method. Structure was solved using Direct Methods (SHEI,XT 2014/4,
Sheldrick,
2014) and refined using SHELXL201 7/ 1 ( Sheldrick, 2017) (full-matrix least-
squares on F2).
Crystal data and refinement conditions are shown in Table 2.. All attempts to
refine peaks of
residual electron density of disordered solvent molecules were unsuccessful.
Therefore the
data were corrected for the contribution of a disordered solvent density using
of the
SQ-LjEEZE procedure as implemented in PLATON. The total solvent accessible
void volume
is 1423 A.
Table 2. Crystal data and structure refinement conditions for Ni-Antit-MOF
Chemical formula C221112Ni0.7506
Mr 416.35
Crystal system, space group Monoclinic, P2Im
Temperature (K) 170
a, b, c (A) 11.7483 (2), 20.6778 (3), 13.1192 (2)
(o) 113.923 (2)
V (A3) 2913.24 (9)
4
Radiation type Cu Ka
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(mm-1) 1.01
Crystal size (mm) 0.10 x 0.08 x 0.05
Diffractometer XtaLAB Synergy, Dualflex, HyPix
Absorption correction Multi-scan
Tmin, Tmax 0.475, 1.000
No. of measured, independent and ob- 28104, 6144, 5300
served [I> 2a(/)[ reflections
Rint 0.078
(sin 0/2)max (A1) 0.630
R[F2 > 2a(F2)], wR(F2), S 0.091, 0.290, 1.14
No. of reflections 6144
No. of parameters 272
H-atom treatment H-atom parameters constrained
Apma,õ Apmin (e A-3) 1.28, -0.58
The powder X-ray diffraction patterns tor C.:u-Auth-MOF and Ni-Anth-MOF were
collected on a Bruker D8 Advance (Bruker AXS GmbH, Karlsruhe, Germany)
diffractometer
equipped with a LynxEye position sensitive detector, using copper radiation
(CiiKõ) at the
wavelength of 1,54180 A. The tube voltage and current were set to 40 kV and 40
mA, respec-
tively. The divergence slit was set at 1.0 mm, and the antiscattering slit was
set at 8.0 nun.
The PXRD patterns were acquired using a scan speed of 025 00.02 going from 3
to 35 on
the 20 scale. See Fig. 5 for PXRD of Cu-Anth-M0F. See Fig. 6 for PXRD of Ni-
Anth-
MOE.
High-resolution dynamic thermal gmvimetric analysis (TGA.). Thermogravimetiie
analysis (TGA) was performed with TG,AA)SC2 (Mettler Toledo). Open 100 L
aluminum
pans were used. Heating of the samples: from 25 to 400 ')C. for Cu-Anth-M0F;
from 25 to
6(X) for Ni-Anth-MOE Heating rate: 10 "C=mirli. Samples of ¨3.3 mg mass
were used,
and the nitrogen flow rate was 100 10 inL=min-1. See Fig. 7 for
thermogravimetric curve for
Cu-Anth-MOF. See Fig. 8 for thermogravimetric curve for Ni-Auth-IWO.F.
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Fluorescence in solution. Solution of MB in water was prepared with the final
concentration J.
nmolitõ pH 7. Fluorescence emission spectrum was recorded with excitation at
290 nrn (Fig.
11).
Solid-state fluorescence. As-synthesized crystals were isolated by filtration,
washed on filter,
-but not dried. Background fluorescence was measured with excitation at 290 nm
(Fig. 12 for
Cu-Anth-MOF and Fig. 14 for Ni-.Antit-M0F). Crystals of MOE were soaked in
ail. solu-
tion of MB for 3 days at room temperature. The crystals were isolated by
filtration and.
washed wi tit water. Solid-state ft uorescence emission spectrum was recorded
with excitation
at 290 MU (Fig. 13 for Cu-Anth-MOF and Fig. 15 for Ni-Anth-MOF). Then host-
guest
complexes of MOF with MB were suspended in water and equal amount of cone, a(F
was
added. Mixture was incubated at 50 C for 8 h. AN insoluble,s were filtered
off, filtrate was
neutralized to pH 7 with aq, satd. NatIC03 and fluorescence emission spectrum
was recorded
with excitation at 290 mu. (Fig. 16 for Cu-Anth-NIOF and Fig. 1.7 for Nii-
.4nth-M0F).
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