Mixed Ligand Coordination Polymers for Metallogelation and Iodine Adsorption

Article abstract of DOI:10.1021/acs.cgd.8b01547

A bis-pyridyl-bis-amide derivative of diphenylmethane (L1) and terephthalate (TA) was combined with a number of metal salts [Cu(II), Zn(II), Ni(II), Co(II), and Cd(II)] in a 1:1:1 molar ratio to generate a series of coordination polymers (CP1A-CP5) which

Full text of DOI:10.1021/acs.cgd.8b01547

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Article
Mixed Ligand Coordination Polymers for
Metallogelation and Iodine Adsorption
Parthasarathi Dastidar, and Swapneswar Mondal
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01547 • Publication Date (Web): 04 Dec 2018
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Page 1 of 12
Crystal Growth & Design
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Mixed Ligand Coordination Polymers for Metallogelation and Iodine
Adsorption
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Swapneswar Mondal and Parthasarathi Dastidar*
School of Chemical Sciences, Indian Association for the Cultivation of Science (IACS), 2A & 2B Raja S. C. Mullick
Road, Jadavpur, Kolkata – 700032, West Bengal, India
Coordination Polymers, Metallogels, Crystal Engineering, Supramolecular Gels, Nanoparticles, Iodine Adsorption
ABSTRACT: A bis-pyridyl-bis-amide derivative of diphenyl methane (L1) and terephthalate (TA) were combined with a
number of metal salts [Cu(II), Zn(II), Ni(II), Co(II) and Cd(II)] in 1:1:1 molar ratio to generate a series of coordination
polymers (CP1A-CP5) which were thoroughly characterized by single crystal X-ray diffraction. All the CPs turned out to
be lattice occluded crystalline solid having 4x4 grid framework structures. Under suitable conditions, the reactants of the
corresponding CPs produced metallogels as envisaged considering a crystal engineering based structural rationale. One of
the CPs, namely CP5 demonstrated the ability to adsorb molecular iodine both in vapor and solution phase. Iodine
adsorption was also found to be reversible as evident from its release in ethanol from both CP5@I2 (vapor) and
CP5@I2(solution). In situ synthesis of silver nanoparticles was also achieved in the gel matrix of L1 without the help of any
exogenous reducing agent.
Introduction. There have been increased research
interests in developing rational approaches to design
supramolecular gels1-6 as they offer potential applications
in various areas of material science.7-12 Supramolecular
gels are visco-elastic materials that comprise a small
amount of gelator(s) and a large volume of solvent(s).
Within a gel network formed due to supramolecular
assembly of the gelator molecules (known as self-
assembled fibrilar networks or SAFiNs13) the solvent
molecules are immobilized due to surface tension or
capillary force action resulting in a solid like materials
called gels. Various non-covalent (supramolecular)
interactions such as hydrogen bonding, halogen bonding,
- stacking, van der Waals interactions, charge transfer
interactions etc. are responsible for the formation of
SAFiNs. Metallogels14-16 are supramolecular gels wherein
demonstrated the link between gels and crystal
engineering31, and generated a large number of gels
displaying intriguing functions by exploiting the merit of
supramolecular synthons in the context of crystal
engineering.32,33 However, this approach is particularly
valid for organogels wherein the solvent is organic and
consequently do not participate in gel network formation.
Metallogels, on the other hand, are usually formed in
aqueous solvents and in here, water being good hydrogen
bond donor as well as acceptor, do participate in gel
network formation. This is quite evident from the crystal
structure analysis of a number of hydrogelators.34-36
We37,38 and others,39 therefore, proposed that compounds
prone to form lattice occluded crystalline solids (LOCS)
are potential target as gelators since in both LOCS and
gel, a large number of solvent molecules are entrapped.
Following this hypothesis, we have designed a number of
metallogels that displayed intriguing functions.17
metal-ligand
coordination
along
with
other
supramolecular interactions takes part in SAFiNs.
Coordination
polymers
(CPs),17,18,19
coordination
Iodine plays crucial role in the area of functional
materials, biomedical applications, environmental
chemistry etc.40,41 For examples, applications of iodine and
its isotopes are found in cancer treatment, and electrical
conductivity.42,43 Iodine isotopes pose an environmental
hazard in nuclear affluent.44-48 Therefore, demand for
materials capable of adsorbing iodine has gained
complexes (CCs),20-22 cross-linked coordination polymers23
are reported to form metallogels. Gels containing metal
nanoparticles also belong to this class.24-26
Gels are believed to be formed due to frustrated or
failed crystallization process wherein
a
solution
containing gelator molecules, under suitable conditions,
takes a kinetically driven path towards meta-stable gels
instead of thermodynamically stable crystals. In the
absence of detail molecular level information of gelation
mechanism, it is understandable that designing gelator
molecule a priori is indeed a difficult task. Nevertheless,
there have been efforts by various groups towards
meeting this goal.27-30 Our group has successfully
increased
interest.
Chalcogenide
aerogels,49
functionalized clays, and silver-based porous zeolitic
materials50,51 for iodine adsorption have been studied
extensively. However, limited adsorption ability, high cost
and environmental issues with these materials created
demand
for
developing
alternative
materials.
Coordination compounds such as CPs possess ability to
adsorb iodine not only in its pore (for porous CPs) but
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also the framework of CPs facilitates iodine adsorption asymmetric unit. The metal center in CP1A displayed a
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through non-covalent interactions involving iodine and
various sorption sites such as -conjugated moiety,
slightly distorted octahedral geometry wherein the axial
sites were coordinated by two pyridyl N atoms of L1 and
the equatorial positions were occupied by O atoms of two
TA (unidentate coordination mode) and two water
molecules. On the other hand, Cd(II) in CP1B displayed
pentagonal bipyramidal geometry; in here, the equatorial
sites were occupied by O atoms of two TA (bidentate
coordination mode) and one water molecule. The relative
orientation of the terminal pyridyl N atoms in both the
structures was syn whereas that of the amide carbonyl O
atoms exhibited anti for CP1A and syn for CP1B. Both the
ligands (L1 and TA) were involved in extended
coordination with Cd(II) metal center resulting in 2D grid
network in both the structures; the grid architecture was
corrugated 2D sheets for CP1A and 2D layered network
for CP1B. The 2D networks were packed in parallel
fashion in both the cases. Except the disordered MeOH,
all the solvates (water) in CP1A were found to be
stabilized in the crystal lattice by hydrogen bonding
interactions involving the amide backbone of L1, metal
bound water and themselves. In CP1B, on the other hand,
the solvate MeOH was found to be tightly held in the
crystal lattice through hydrogen bonding interactions
involving amide functionality of L1 (Figure 1 and 4).
pyridyl,
hydroxyl,
ether,
amino
functionalities
(encouraging halogen bonding) etc.52-61
With this background, we, set out to synthesize a series
of CPs by reacting a bis-pyridyl-bis-amide ligand having
diphenylmethane backbone (L1), terephthalate (TA) and
various metal ions [Cu(II), Zn(II), Ni(II), Co(II) and
Cd(II)] in 1:1:1 molar ratio. While the expected 4x4 grid
framework structure having hydrogen bond capable
amide backbone of L1 in the CPs is expected to occlude
solvent molecules in its crystal lattice thereby forming
LOCS, the aromatic  backbone of both the ligands (L1
and TA) might help adsorb iodine. Therefore, the
resulting CPs are expected to form metallogels under
suitable conditions and also the CPs might have ability to
adsorb iodine. We report the solvothermal synthesis of a
series of CPs (CP1A-CP5) derived from L1, TA and the
metal salts in DMF/methanol/water and their thorough
characterization by single crystal X-ray diffraction (SXRD)
(Scheme 1). All the CPs turned out to be LOCS as
envisaged. Except the CP derived from Cu(II), all the
other CPs displayed ability to form metallogel (MG1,
MG2, MG4 and MG5) in DMF/water (1:1 v/v) at room
temperature. The Co(II) CP i.e. CP5 displayed the ability
to adsorb iodine both from solution as well as from vapor.
Iodine adsorption by CP5 was found to be reversible.
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Figure 1. Crystal structure illustrations of CP1A and CP1B
along with their corresponding network topology62,63
Scheme 1. Schematic representation of the synthesis of
Crystal structures of CP2A and CP2B. Like
CP1A/CP1B, these two CPs were also pseudopolymorph as
evident from their different space group (monoclinic C2/c
for CP2A and P-1 for CP2B) and different lattice occluded
solvate content (3H2O+MeOH for CP1A and
4H2O+MeOH for CP2B). The Ni(II) metal center in CP2A
was located on a center of inversion thereby displaying
perfect octahedral coordination environment; the axial
positions were occupied by water molecules whereas the
equatorial sites were coordinated by two O atoms of TA
(unidentate coordination mode) and two N atoms of
pyridyl moiety of L1. On the other hand, the metal center
in CP2B showed slightly distorted octahedral geometry
displaying identical coordination environment of CP2A.
CPs and metallogels
Results and Discussions. Single crystals of the CPs
obtained by solvothermal crystallization were subjected
to SXRD (Table 1, see experimental section).
Crystal structures of CP1A and CP1B. The
coordination polymers CP1A and CP1B were
pseudopolymorphs because CP1A crystallized in the
triclinic space group P-1 whereas CP1B displayed the
orthorhombic space group Pbca and the lattice occluded
solvents were different in these cases; while CP1A
contained three water and one MeOH (disordered around
a center of inversion) as lattice occluded solvates, CP1B
contained only one MeOH in the corresponding
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Crystal Growth & Design
The ligand L1 adopted anti-anti and anti-syn
experimental patterns obtained from bulk crystals (Figure
S13-19, supporting information) Moreover,
thermogravimetric analysis strongly supported the
solvent content as observed in SXRD analysis (Figure S20-
26, supporting information).
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conformation for CP2A and CP2B, respectively. The
coordination network structures in both cases may best
be described as 2D sheet that were packed in parallel
fashion. The lattice occluded solvent molecules were
found tightly held in the lattice via hydrogen bonding
interactions with the amide backbone of the ligand L1
(Figure 2 and 4).
.
Thus, isolation and characterization of these CPs
clearly established that the network structures were 2D
and the hydrogen bond capable backbone (amide) of L1
played a crucial role in stabilizing the lattice occluded
solvents through hydrogen bonding interactions as
envisaged (Figure 4).
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Figure 2: Crystal structure illustrations of CP2A and CP2B
along with their corresponding network topology62,63
Crystal structures of CP3, CP4 and CP5. These CPs
along with CP2B having identical space group (triclinic,
P-1) and near identical cell dimensions (see Table 1) were
isomorphous and therefore, they displayed identical
crystal packing. The corresponding metal centers Cu(II),
Zn(II) and Co(II) for CP3, CP4 and CP5, respectively
being located on a general position displayed slightly
distorted octahedral geometry wherein the axial positions
were occupied by water molecules and the equatorial sites
were coordinated by two N atoms of L1 and two O atoms
of TA (unidentate coordination mode). The ligand L1
adopted anti-syn configuration in all the cases as also
observed in CP2B. The coordination networks were 2D
sheet in all these structures. As expected, the lattice
occluded solvents (3H2O, 3H2O+MeOH and H2O+MeOH
for CP3, CP4 and CP5, respectively) were found to be
involved in hydrogen bonding with the amide backbone
of the ligand L1 (Figure 3 and 4).
Figure 4. Illustration of crystal packing of all the CPs
displaying lattice occluded solvents (color code: H2O –
orange in CP2A, CP2B, CP3 and CP4; H2O – yellow in CP1A
and CP5; MeOH – magenta)
Metallogelation. The foregoing discussions on the
crystal structures of the CPs clearly indicated that it was
worthwhile to explore metallogelation with the reactants
of the CPs i.e. L1, TA and the corresponding metal salts.
Before exploring metallogelation, we first studied the
gelation properties of L1. It turned out that L1 was an
excellent gelator of DMSO/water (3:2 v/v) with a
minimum gelator concentration of 4 wt %. Guided by the
crystal structures of the CPs, we reacted L1, TA and the
corresponding metal salt in 1:1:1 molar ratio in DMF/water
(1:1 v/v) that produced metallogels instantaneously after
5-10 minutes of sonication under ambient conditions
except for Cu(NO3)2 as evident from tube inversion test
(Table 2, Scheme 1, see experimental section).
Rheology. More conclusive data were obtained when
these metallogels were subjected to dynamic rheology
(Figure 5). Gel being visco-elastic material is expected to
display non Newtonian behavior in rheological studies.
Frequency sweep plot wherein elastic modulus (Gˊ) and
viscous or loss modulus (Gˊˊ) are plotted against the
frequency ( rad/s) should typically display the following
behavior for a gel sample: (a) Gˊ must be much larger
than Gˊˊ and (b) Gˊ should be frequency invariant
throughout the entire frequency range. Frequency sweep
data for the aqueous gel of L1 and all the metallogels
carried out at a fixed strain of 0.1 % (suggested by
amplitude sweep experiments, Figure S31) displayed the
characteristic signature of visco-elastic materials
Figure 3. Crystal structure illustrations of CP4 and the
corresponding network topology62,63; CP3 and CP5 (being
isomorphous to CP4) are not shown.
It may be mentioned that the crystalline phase purity of
all the crystals was reasonably high as the simulated
powder diffraction patterns matched well with that of the
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CPs.65,66 In solution phase, CP5 (10 mg) was kept
confirming that they were indeed gels. Tan  (Gˊˊ/ Gˊ)
values for all the gels were greater than 0.1 (Tan  0.23-
0.42) indicating that the gels were significantly strong.
The average Gˊs in the linear visco-elastic region were
within the range of ~2-237 kPa (Table 2).
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immersed in I2 solution in pet ether (3 mL, 5 mmol) in a
closed container for 1 day. Once again visual observation
(turning dark pink I2 solution to light pink) was indicative
of I2 adsorption. The I2 adsorbed solid CP5@I2(solution)
was then filtered and washed several times with pet ether
to remove adhered I2. TGA data indicated that 30.3 wt %
adsorption of I2 by CP5 was achieved in solution phase.
The value attributed to ~0.9 molecule of I2 adsorbed per
formulae unit of CP5. The data were found consistent
with that displayed by quite a few CPs.65-68 (Figure 7)
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Figure 5. Frequency sweep plot for all the gels
Microscopy. To visualize the morphology of the gel
network, we carried out TEM imaging of the dried gels
(see experimental section). Several micrometer long plate
like morphology was observed in the TEM images in dried
gels of L1, MG1 and MG4. Selected area electron
diffraction (SAED) of the microplates observed under
TEM did not show any diffraction confirming that they
were not microcrystals precipitated out during TEM
sample preparation. Although highly entangled fibrilar
morphology is typical for supramolecular gels, such tape
type of morphology as observed here is not uncommon
(Figure 6).64 It may be noted that TEM images of MG2
and MG5 could not be recorded due to the possible
magnetic properties arising because of Ni(II) and Co(II) in
the metallogel.
Figure 7. visual observation of I2 adsorption and TGA profile
of I2 release.
FT-IR spectrum of CP5, CP5@I2(vapor) and
CP5@I2(solution) were compared; the spectra were
nearly superimposable suggesting weak interactions of I2
with CP5. PXRD patterns of as synthesized CP5,
CP5@I2(vapor) and CP5@I2(solution) were also
compared; all the patterns were in good agreement
indicating no phase change due to I2 adsorption which
further supported physical adsorption of I2 through weak
interactions (Figure 8).
Figure 6. TEM images of the gels (inset – SAED).
Iodine adsorption and release. All the CPs were
subjected to I2 adsorption both in vapor phase and in
solution. Except CP5, all the CPs failed to show any I2
adsorption ability in both the phases as evident from
visual observation. In a typical experiment in vapor phase,
CP5 (10 mg) was subjected to I2 vapor in a closed
container for 1 day at room temperature. Brown solid CP5
turned dark pink (nearly black in naked eyes) solid
CP5@I2(vapor) which was thoroughly washed with pet
ether to remove excess I2 adhered to the surface of the
powdered sample of CP5. The amount of I2 adsorbed by
CP5 was quantified by thermogravimetric analysis (TGA)
that showed 21.4 wt % adsorption. Thus, per formulae
unit of CP5 was able to adsorb ~0.6 molecules of I2. The
data were comparable to that observed for many reported
Figure 8. FT-IR and PXRD of CP5 under various conditions.
Release of I2 from the iodine adsorbed CP5 (both
phases) was easy and spontaneous in polar organic
solvents like EtOH. For this purpose,
1 mg of
CP5@I2(vapor)/ CP5@I2(solution) was immersed in 3
mL of EtOH. Colorless EtOH layer gradually turned
brown within 4 h. In situ UV-vis absorption showed linear
increase of the absorbance at 220-400 nm suggesting
steady release of I2 from iodine adsorbed CP5 (Figures
S32-33, supporting information)
Synthesis of Ag nanoparticles within the gel matrix
of L1.
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Crystal Growth & Design
We also considered exploring the possibility of
both vapor and solution phase. Thus a series of
CPs was achieved that displayed multi-functional
properties like metallogelation and molecular
iodine adsorption. The aqueous gel of L1 was
also able to produce AgNPs without the help of
any exogenous reducing agent.
1
generating metal nanoparticles (MNPs) in the gel matrix
of L1. Owing to their quantum-size effects and large
surface-to-volume ratio, MNPs are promising materials
for catalysis.69 Although access to MNPs is usually
through reduction of a target metal salt with the help of
external reducing agent, supramolecular gels wherein the
gelator molecules have amide/urea/thiourea moieties are
known to produce MNPs in situ without the help of
exogenous reducing agent.70,71,72 For generating silver
nanoparticles, aqueous solution of AgNO3 (2 mg in 2 mL
of water) was placed over a gel bed of L1 in DMSO/H2O
(3:2). The solution was kept in dark at room temperature
for 24 h. The color transition was observed from white
opaque gel to light-brown gel indicating the formation of
Ag nanoparticles (AgNPs) which were further studied by
UV-vis and TEM. A peak at  = 440 nm in the UV-vis
spectrum of gel containing MNP dispersed in DMSO at
room temperature was due to the characteristic surface
plasmon absorption band of AgNPs. FEG-TEM images of
dried gel of L1 containing AgNPs clearly showed that the
MNPs were adhered to the surface of plate like gel
networks. Presumably the bis-amide backbone of L1 and
visible light played a crucial role in reducing Ag ion to
generate AgNPs within the gel matrix (Figure 9).
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Experimental Section
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Materials
and
Methods
for
Physical
Measurements. All reagents and chemicals are
purchased from commercial sources and used without
further purification. FT-IR spectra were recorded on a FT-
IR instrument (Perkin Elmer, FT-IR Spec-trometer,
Spectrometer Two). Elemental analyses were performed
on Perkin Elmer Precisely, Series-II, CHNO/S Analyser-
2400. TGA experiments were done on a SDT Q Series 600
Uni-versal VA.2E TA instrument. X-ray powder diffraction
patterns were recorded on a Bruker AXS D8 Advance
Powder (CuK radi-ation,
λ
=
1.5418 Å) X-ray
diffractometer. TEM images were rec-orded using a JEOL
instrument (JEM-2100F; JEM-2010) with 300 mesh copper
TEM grid. UV/Vis spectroscopic measurements were
performed on a Hewlett–Packard 8453 diode array
spectro-photometer equipped with a Peltier temperature
controller. NMR spectra were carried out using 400/500
MHz spectrometer (Bruker Ultrasheild Plus- 400/500).
Synthesis of L1. Nicotinoyl Chloride hydrochloride
(1.78 g, 10 mmol) and dry triethyl amine (1.5 mL) were
dissolved in dry DCM (250 mL) in a round bottom flask
(500 mL). Then 4,4'-methylenedianiline (1 g, 5 mmol) in
dry DCM (5 mL) were added drop wise under nitrogen
atmosphere and the reaction mixture was stirred for 12 h
at reflux temperature. Obtained precipitate was filtered
and washed several times with dry DCM. The ligand L2
was isolated (Yield 67%) as white precipitate followed by
drying in vacuum.
L1: 1H NMR (500 MHz, DMSO) δ 10.39 (s, 1H), 9.09 (s,
1H), 8.75 (d, J = 5 Hz, 1H), 8.28 (d, J = 5 Hz, 1H), 7.69 (d, J
= 10 Hz, 1H), 7.56 (dd, J = 10, 5 Hz, 1H), 7.23 (d, J = 10 Hz,
1H), 3.91 (s, 2H) (see supporting information Figure S1);
13C NMR (100 MHz, DMSO) δ 163.87, 152.02, 148.59, 137.11,
136.79, 135.34, 130.59, 129.07, 128.85, 123.48, 120.53 (see
supporting information Figure S1). ESI-MS-(MeOH):
calculated for [M+H]+ is 409.16, found 409.08 (see
Figure 9. (clockwise) Synthesis of AgNPs in gel matrix of L1;
TEM images of AgNPs adhered to the gel network; EDX
displaying existence of Ag; typical surface plasmon spectra of
AgNPs.
휐,
supporting information Figure S3). FT-IR ( cm-1): 3347,
1662, 1645, 1598, 1525, 1511, 1407, 1287, 1267, 820, 740, 706,
688, 511 (see the Supporting Information, Figure S4).
wUhpc4iDdHemnPalbfsItTA0Norysnhoieuaphb.xdmonyle8is,fargmbhwosarVMRigPmdotcenhrpsTichelnd5caoetislnfcwNortgu.isdcomehalkrwT/yfcgApdnaerhmSfve.h-oagVurntcihsrbteloPrciEteadshbnledpOToaigvlytmckdnomilrf2szhoedguraMdtfeskhtifasniy–gafebnhtraleob.elietba9ul,nytegdo=nhlctlr
Conclusions. The results presented herein clearly
emphasized the importance of structural rationale
based on which the CPs were designed. All the
CPs (CP1A-CP5) were LOCS and the
corresponding reactants under suitable conditions
produced metallogels (MG1, MG2, MG4 and
MG5) as envisaged. One of the CPs namely CP5
displayed the ability to adsorb and release I2 from
Synthesis of the Coordination Polymers.
[{Cd(µ-L1)(µ-TA)(H2O)2} ・ 3H2O·MeOH]∞ (CP1A): A
mixture of L1 (20 mg, 0.05 mmol) and disodium
terephthalate (Na2TA; 10 mg, 0.05 mmol) in DMF (2 mL)
and MeOH (2 mL) was added to an aqueous solution (1
mL) of Cd(NO3)2·4H2O ( 15 mg, 0.05 mmol) in screw
capped plastic vial (25 mL) and heated at 80˚C for 48 h in
an oven. The mixture was slowly cooled to rt. and
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colorless block-shaped crystals were formed, which were Metallogelation. A clear solution of L1 in DMF was
-1
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휐,
mixed with an aqueous solution containing Na2TA and
the corresponding metal salt in a sonicator (5-10 mins) at
ambient condition that resulted in metallogel.
filtered and dried in air. FT-IR ( cm ): 3270, 1658, 1604,
1538, 1505, 1410, 1376, 1325, 1047, 827, 753, 509.
[{Cd(µ-L1)( µ-TA)(H2O)} ·MeOH] ∞ (CP1B): A mixture of
L1 (20 mg, 0.05 mmol) and disodium terephthalate
(Na2TA; 10 mg, 0.05 mmol) in DMF (1 mL) and MeOH (2
mL) was added to an aqueous solution (3 mL) of
Cd(NO3)2·4H2O (15 mg, 0.05 mmol) in screw capped
plastic vial (25mL) and heated at 80˚C for 48 h in an oven.
The mixture was slowly cooled to rt. and colorless block-
shaped crystals were formed, which were filtered and
Transmission electron Microscopy. Small amount
of gel sample was smeared on a 300 mesh Cu grid and
dried under vacuum at room temperature for 1 day. TEM
images were recorded without staining.
Single Crystal X-ray Crystallography. Single
crystal X-ray data were collected by using Mokα
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(λ=0.7107Å) radiation on
a
BRUKER APEX II
흊,
dried in air. FT-IR ( cm-1): 3292, 1662, 1608, 1544, 1506,
diffractometer equipped with CCD area detector. Data
collection and data reduction were done using APEX II
package software. The structures were solved by using
direct methods and refined in a routine manner. Data of
CP2A and CP3 were collected in Bruker D8VENTURE
Micro focus diffractometer equipped with PHOTON II
detector (Mo kα (λ=0.7107Å). Data collection and data
reduction were done by using APEX3 software package in
a routine manner. Final refinement and CIF finalization
were carried out by using OLEX2 version 1.2.9. In all
cases, the non-hydrogen atoms were treated
anisotropically whereas most of the hydrogen atoms were
geometrically fixed; wherever possible, the hydrogen
atoms associated with guest solvent molecules were
located on difference Fourier map and refined. CIFs files
has been deposited to The Cambridge Crystallographic
Data Centre (CCDC). CCDC 1863205-1863211 contain the
supple-mentary crystallographic data for this paper.
These data can be obtained free of charge from CCDC.
1410, 1385, 1328, 1051, 823, 775, 754, 513.
[{Ni(µ-L1)( µ-TA)(H2O)2} .3H2O·MeOH]∞ (CP2A): CP2A
was synthesized by following the procedure used for
synthesizing CP1A; in this case, Ni(NO3)2·6H2O (14.5 mg,
0.05 mmol) was used. Upon slow cooling to rt., green
block shape crystals were formed, which were filtered and
흊,
dried in open air. FT-IR ( cm-1): 3304, 1673, 1603, 1541,
1510, 1482, 1377, 1326, 1017, 752, 696, 597, 507).
[{Ni(µ-L1)( µ-TA)(H2O)2} .4H2O·MeOH]∞ (CP2B): CP2B
was synthesized by following the procedure used for
synthesizing CP1B; in this case Ni(NO3)2·6H2O (14.5 mg,
0.05 mmol) was used. Upon slow cooling to rt., green
block shape crystals were formed, which were filtered,
흊,
washed with MeOH and dried in open air. FT-IR ( cm-
1):3300, 1657, 1603, 1548, 1502, 1377, 1323, 1035, 832, 753, 505.
[{Cu(µ-L1)( µ-TA)(H2O)2} .3H2O]∞ (CP3). CP3 was
synthesized by following the procedure used for
synthesizing CP1A; in this case Cu(NO3)2·3H2O (12 mg,
0.05 mmol) was used . Upon slow cooling to rt., blue
colored block shape crystals were formed, which were
filtered and washed with MeOH and dried in open air.
Powder X-ray Diffraction. A thin layer made on a
glass slide from bulk powdered sample (~15 mg) was used
for data collection using Bruker AXS D8 Advanced
powder diffractometer (Cukα
radiation, λ=1.5406Å)
휐,
FT-IR ( cm-1): 3389, 1661, 1604, 1543, 1505, 1410, 1367, 1327,
equipped with super speed LYNXEXE detector with a scan
speed 0.3 sec/step for scan range of 2(5˚-35˚).
1056, 826, 776, 751, 512.
[{Zn(µ-L1)( µ-TA)(H2O)2} .3H2O·MeOH]∞ (CP4). CP4
was synthesized by following the procedure used for
synthesizing CP1A; in this case Zn(NO3)2·6H2O (15 mg,
0.05 mmol) was used. Upon slow cooling to rt., colorless
block shape crystals were formed, which were filtered and
ASSOCIATED CONTENT
Supporting Information. Supporting information is
available free of charge via the Internet at
http://pubs.acs.org.
흊,
washed with MeOH and dried in open air. FT-IR ( cm-
1): 3313, 1664, 1609, 1505, 1374, 1330, 1198, 824, 755, 642, 511.
1H, 13C NMR, FT-IR, HRMS, ORTEP plots, hydrogen
bonding table, TGA, PXRD patterns, Rheological data,
UV-vis spectra.
[{Co(µ-L1)(µ-TA)(MeOH)(H2O)} .H2O·MeOH]∞ (CP5).
CP5 was synthesized by following the procedure used for
synthesizing CP1A; in this case Co(NO3)2·6H2O (14.5 mg,
0.05 mmol) was used. Upon slow cooling to rt., pink
colored block shape crystals were formed, which were
filtered and washed with MeOH and dried in open air.
Author information
Corresponding author
흊,
FT-IR ( cm-1):3283, 1660, 1605, 1542, 1503, 1383, 1326, 1275,
*E-mail: ocpd@iacs.res.in
1048, 751, 512.
ACKNOWLEDGMENT
Gelation. L1 (40 mg) was dissolved in DMSO (0.6 mL)
in a glass vial (3 mL) by heating on a hot plate. The
solution was cooled to rt. to which water (0.4 mL) was
added resulting in instant gelation (MGC 4 wt %) as
evident from tube inversion and rheological data. It was
found to be thermoreversible over a few cycles.
SM thanks UGC for research fellowship. P.D. thanks DST
(Grant No. EMR/2016/000894) for financial support. P.D.
indebted to Professor Israel Goldberg for giving him
opportunity to work as a post-doctoral fellow under his
supervision during the year 1994-1996.
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Table 1. Crystallographic data and structure-refinement parameters for polymers CP1A–CP5.
1
2
3
4
5
Identification
code
CP1A
CP1B
CP2A
CP2B
CP3
CP4
CP5
1863209
CCDC
1863206
1863211
1863210
1863205
1863207
1863208
Empirical formula C33.5H26CdN4O11.25 C34H30CdN4O8 C34H30N4NiO11 C34H24N4NiO13 C33H28CuN4O11 C33.25H28N4O11.5Zn C35H30CoN4O10
6
7
8
9
Formula weight
776.98
296.15
735.02
296.15
729.33
142.81
755.28
720.13
732.96
298
725.56
Temperature/K
100.01
298
120.22
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17
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19
20
21
22
23
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25
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46
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49
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Crystal system
Space group
a/Å
triclinic
P-1
orthorhombic monoclinic
triclinic
P-1
triclinic
P-1
triclinic
P-1
triclinic
P-1
Pbca
C2/c
9.539(6)
11.408(7)
17.330(11)
85.615(10)
85.125(10)
66.829(9)
1725.5(19)
2
11.4197(15)
20.410(3)
26.422(4)
90
18.505(8)
18.012(8)
21.407(9)
90
9.2545(10)
11.1448(12)
17.409(2)
92.728(4)
90.397(4)
113.308(4)
1646.5(3)
2
9.2658(8)
11.0361(9)
17.4680(13)
92.978(3)
90.487(3)
114.101(2)
1627.5(2)
2
9.389(6)
11.324(7)
17.511(11)
92.451(9)
90.647(9)
113.400(9)
1706.4(19)
2
9.3588(4)
11.2448(5)
17.4321(7)
91.987(3)
90.278(3)
113.882(3)
1676.08(13)
2
b/Å
c/Å
α/°
β/°
90
111.239(6)
90
γ/°
90
Volume/Å3
Z
6158.3(14)
8
6651(5)
8
ρcalcg/cm3
μ/mm-1
F(000)
1.495
1.586
1.457
1.523
1.47
1.427
1.438
0.698
0.77
0.651
0.665
0.739
0.787
0.577
786
2992
3024
776
742
755
750
Crystal size/mm3 0.36 × 0.15 × 0.1
0.3 × 0.21 × 0.28 × 0.16 × 0.31 × 0.22 × 0.9 × 0.32 × 0.2 0.25 × 0.12 × 0.08 0.34 × 0.25 ×
0.12
0.12
0.15
0.18
Radiation
MoKα
0.71073)
(λ
= MoKα (λ = MoKα (λ = MoKα (λ = MoKα (λ = MoKα
(λ
= MoKα (λ
=
0.71073)
0.71073)
0.71073)
0.71073)
0.71073)
0.71073)
2Θ range for data 2.362 to 40.364
collection/°
3.082 to 53.632 3.27 to 51.12
4.512
46.848
to 4.552 to 54.598 2.328 to 39.356
3.964 to 52.812
Index ranges
-9 ≤ h ≤ 9, -11 ≤ k -14 ≤ h ≤ 14, - -22 ≤ h ≤ 22, - -10 ≤ h ≤ 9, -11 -11 ≤ h ≤ 11, -14 -8 ≤ h ≤ 8, -10 ≤ k -11 ≤ h ≤ 11, -13 ≤
≤ 11, -16 ≤ l ≤ 16
25 ≤ k ≤ 25, -32 21 ≤ k ≤ 21, -25 ≤ k ≤ 12, -19 ≤ l ≤ k ≤ 14, -20 ≤ l ≤ 10, -16 ≤ l ≤ 16
k ≤ 14, -21 ≤ l ≤
21
≤ l ≤ 33
≤ l ≤ 25
≤ 19
≤ 22
Reflections
collected
26304
75322
80080
14161
20088
15266
21989
Independent
reflections
3297
0.0958, Rsigma = 0.0576,
0.0508] Rsigma
[Rint = 6523
[Rint = 6210
0.0923,
Rsigma
[Rint = 4759
[Rint = 7271
[Rint = 3009
[Rint = 6808
Rsigma = 0.0869, Rsigma
0.1142]
[Rint
=
=
0.0569,
Rsigma
0.0868, Rsigma = 0.0693,
0.1237]
=
=
=
0.0514]
0.0354]
0.0446]
0.0696]
Data/restraints/pa 3297/0/448
rameters
6523/0/427
6210/0/461
4759/0/459
7271/0/443
1.067
3009/0/449
1.053
6808/4/446
0.988
Goodness-of-fit on 1.082
F2
0.936
1.024
1.129
Final
R
indexes R1 = 0.0545, wR2 = R1 =
0.0436, R1 = 0.0444, R1 =
wR2 = 0.2087 wR2 = 0.1165 wR2 = 0.2384 wR2 = 0.2220
0.0916, R1 =
0.0898, R1 =
0.0650, R1 =
0.0685,
[I>=2σ (I)]
0.1523
wR2 = 0.2071 wR2 = 0.1757
Final
R
indexes R1 = 0.0726, wR2 = R1 =
0.0722, R1 = 0.0800, R1 = 0.1157, R1 = 0.1570, R1 =
0.0850, R1 =
0.1229,
[all data]
0.1684
wR2 = 0.2294
wR2 = 0.1409 wR2 = 0.2535 wR2 = 0.2666 wR2 = 0.2283
wR2 = 0.2097
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Crystal Growth & Design
Table 2. Gelation and Rheology table of various metallogels.
1
2
Gel
Metal Salt
Ligand (L1)
Co-Ligand (TA)
MGC (wt%) Critical Strain G'
G"/G'
3
(%)
4
5
6
7
8
9
MG1
MG2
MG4
MG5
Cd(NO3)2;
6 mg
3 mg
5.4
7.74
2.37*105
9.32*104
7.69*104
2.03*103
0.24
0.23
0.39
0.42
4.5 mg (0.014mmol)
(0.014mmol)
(0.014mmol)
Ni(NO3)2 ;
6mg
(0.014mmol)
3 mg
5.3
70.08
8.73
7.01
4.27 mg (0.014mmol)
(0.014mmol)
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Zn(NO3)2 ;
6 mg
3 mg
5.36
5.31
4.4 mg (0.014mmol)
(0.014mmol)
(0.014mmol)
Co(NO3)2;
6 mg
3 mg
4.28 mg (0.014mmol) (0.014mmol)
(0.014mmol)
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Crystal Growth & Design
Page 12 of 12
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SYNOPSIS TOC. A crystal engineering based approach has been adopted to generate a series of coordination
polymers that displayed both metallogelation and I2 adsorption
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Insert Table of Contents artwork here
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