Structural diversity in six mixed ligand Zn(II) metal-organic frameworks constructed by rigid and flexible dicarboxylates and different N, N′ donor ligands

Article abstract of DOI:10.1021/acs.cgd.7b01270

Three different N, N′-donor ligands with Zn(NO₃)₂·6H₂O and two different dicarboxylates, flexible succinate (suc) and rigid fumarate (fum) afforded six different metal-organic frameworks (MOFs). Among the N, N′-donor ligands, one bent 1, 4-bis(3-pyridyl)-2, 3-diaza-1, 3-butadiene (3-bpdb) gives two isostructural two-dimensional MOFs, {[Zn(3-bpdb)(suc)]·(H₂O)₂}_n (1) and {[Zn(3- bpdb)(fum)(H₂O)₂]}_n (2). The use of a straight N, N′-donor ligand, i.e., 1, 4-bis(4- pyridyl)-2, 3-diaza-1, 3-butadiene (4-bpdb), results in two three-dimensional (3D) MOFs, {[Zn₄(4-bpdb)₂(suc)3(OH)₂]·5(H₂O)}n (3) and {[Zn(4-bpdb)(fum)]·(H₂O)₂}_n (4). Here, 3 is a pillared layer structure, whereas 4 has a 5-fold interpenetrated dimondoid network. For both the bent and straight N, N′-donor ligands an imine alike motif is embedded in the structure. When this motif is replaced by a C-C double bond by using the ligand 1, 2-bis(4-pyridyl)ethylene (bpee), it produces two MOFs, {[Zn(bpee)(suc)]₂·(H₂O)₃}_n (5) and {[Zn2(bpee)2(fum)2]·(H₂O)}n (6), having a similar structural relation like 3 and 4 respectively, 5 with a pillared layer structure and 6 with a 5-fold interpenetrated diamondoid network. All the compounds have been thoroughly characterized by powder X-ray diffraction (PXRD), elemental analysis, infrared (IR) spectroscopy, UV-vis spectroscopy, and thermogravimetric analyses. Gas/solvent vapor sorption studies have been carried out for compounds 3-6, which have 3D structures. In the case of 3, an interesting reversible crystalline to crystalline transformation was observed which has been thoroughly studied by PXRD analysis, IR spectroscopy, and UV-vis spectroscopy. Solid state emission spectral analysis for all the complexes was performed at room temperature.

Full text of DOI:10.1021/acs.cgd.7b01270

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Article
Structural Diversity in Six Mixed Ligand Zn(II) Metal-
Organic Frameworks Constructed by Rigid and Flexible
Dicarboxylates and Different N, N# Donor Ligands
Arijit Halder, Biswajit Bhattacharya, Fazle Haque, and Debajyoti Ghoshal
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01270 • Publication Date (Web): 24 Oct 2017
Downloaded from http://pubs.acs.org on October 26, 2017
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Structural Diversity in Six Mixed Ligand Zn(II) MetalꢀOrganic
Frameworks Constructed by Rigid and Flexible Dicarboxylates and
Different N, N′ Donor Ligands
Arijit Halder, Biswajit Bhattacharya, Fazle Haque and Debajyoti Ghoshal*
Department of Chemistry, Jadavpur University, Jadavpur, Kolkata, 700 032, India
Eꢀmail: dghoshal@chemistry.jdvu.ac.in
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_
__________________________________________________________________________
ABSTRACT
3 2 2
Three different N,N′ꢀdonor ligands with Zn(NO ) ·6H O and two different dicarboxylates,
flexible succinate (suc) and rigid fumarate (fum) afforded six different metalꢀorganic
frameworks (MOFs). Among the N,N′ꢀdonor ligands, one is bent 1,4ꢀbis(3ꢀpyridyl)ꢀ2,3ꢀ
diazaꢀ1,3ꢀbutadiene (3ꢀbpdb), gives two isostructural 2D MOFs, {[Zn(3ꢀbpdb)
(
suc)].(H
ligand, ie 1,4ꢀbis(4ꢀpyridyl)ꢀ2,3ꢀdiazaꢀ1,3ꢀbutadiene (4ꢀbpdb) results two 3D MOFs, {[Zn
bpdb) (suc) (OH) ].5(H O)} (3) and {[Zn(4ꢀbpdb)(fum)].(H O) (4). Here, 3 is a pillared
2
O)
2
}
n
(1) and {[Zn(3ꢀbpdb) (fum) (H
2
O)
2
]}
n
(2). The use of straight N,N′ꢀdonor
4
(4ꢀ
2
3
2
2
n
2
2 n
}
layer structure whereas 4 has fivefold interpenetrated dimondoid network. For both the bent
and straight N,N′ꢀdonor ligands there are imine alike motif is embedded in the structure.
When this motif is replaced by CꢀC double bond by using the ligand, the ligand 1,2ꢀbis(4ꢀ
pyridyl)ethylene (bpee), it produces two MOFs, {[Zn(bpee)(suc)]
2
.(H
(6), having similar structural relation like 3 and 4 respectively,
with pillared layer structure and 6 with fiveꢀfold interpenetrated dimondoid network. All
2 3 n
O) } (5) and
{
2 2 2 2 n
[Zn (bpee) (fum) ].(H O)}
5
the compounds have been thoroughly characterized by powder Xꢀray diffraction (PXRD),
elemental analysis, infrared (IR) spectroscopy, UVꢀvis spectroscopy, thermogravimetric (TG)
analyses. The gas/solvent vapor sorption studies have been carried out for compounds 3ꢀ6
those having 3D structures. In case of 3 an interesting reversible crystalline to crystalline
transformation was observed which has been thoroughly studied by PXRD analysis, IR and
UVꢀvis spectroscopy. Solid state emission spectral analysis for all the complexes has been
performed at room temperature.
_
__________________________________________________________________________
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INTRODUCTION
From the past decade, metalꢀorganic frameworks (MOFs) have remained in the effective
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domain of interest for the chemists, due to their fascinating property as well as their
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ꢀ20
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applications in several areas of modern importance.
The structureꢀproperty relationship
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of these MOFs are one of the major criteria for the investigation of such system for their
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possible real world applications. In connection to that it has been found that although, some
of the physical properties of MOFs have been well interpreted on the basis of their
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structures,
but many of those are yet to know. It has been also observed that the careful
design with the use of suitable linkers/coꢀlinkers along with appropriate metal ions may
originate materials with desired structural arrangement which will endorse specific
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application of interest as well
. In a MOF, structural arrangement of the building unit and
the resultant overall framework topology is generally the key factor for the bulkꢀproperty of
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that particular system and that is why it is always important to analyze the topology of the
system. Therefore, logical design of MOFs with the use of well established strategies of
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reticular chemistry,
i.e. through judicious metalꢀligand combination; produces recurrent
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structural diversity with captivating topologies
and tunable properties
for the
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achievement of next generation materials.
It is worth to mention that the MOFs with various functional pores, always remained in the
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,4,9
limelight for their various applications
and in the synthesis of such MOFs, the use of
multiꢀ carboxylic acid donors and pyridylꢀcontaining coꢀligands have been proven to be an
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efficient strategy.
Successful synthesis of the materials incorporating the aforesaid verity
of ligands will serve the purpose of design and also important to classify the core architecture
3
3ꢀ35
or the topologies.
The ligands with acyclic multiꢀcarboxylate donors provide
26,36
topologically appealing structures,
and the employment of pyridyl coꢀlinkers can enhance
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7
this diversity in a multiplicative manner. In addition to that, on changing the position of
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donor atom and/or introduction of double bond, and/or atom replacement in a ligand
motif may enhance functionality as this effectively changes the coordination pattern and
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hence the nature of bulk or surface property of the system.
On the other hand, type of
metal ion is also an active factor to create the overall structure, affecting functionality as
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well.
It has been observed that the Zn(II) containing MOFs are found with enormous
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possibility of various application like host–guest chemistry,
luminescent materials,
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OLED or NLO materials,
heterogeneous catalysis
so on and so forth.
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Scheme 1. Synthetic outline of complexes 1ꢀ6
Scheme 2. Ligand used for the synthesis of complexes 1ꢀ6
With an attempt for a detailed investigation of the above mentioned understanding, Zn(II) has
been chosen as the metal centre in this present work and we have synthesized six MOFs
(
Scheme 1) with three different N, N´ donor ligands and a flexible and rigid dicarboxylate
namely succinate and fumarate respectively (Scheme 2). The use of a bent coordinating 1,4ꢀ
bis(3ꢀpyridyl)ꢀ2,3ꢀdiazaꢀ1,3ꢀbutadiene (3ꢀbpdb) along with succinate (suc) and fumarate
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(fum) results the formation of two isostructural two dimensional MOFs, {[Zn(3ꢀbpdb)
(
suc)].(H O) } (1) and {[Zn(3ꢀbpdb)(fum)(H O) ]} (2). The use of straight chain 1,4ꢀbis(4ꢀ
2 2 n 2 2 n
pyridyl)ꢀ2,3ꢀdiazaꢀ1,3ꢀbutadiene (4ꢀbpdb), along with the same dicarboxylates used in
previous case results the formation of three dimensional MOFs {[Zn (4ꢀ
bpdb) (suc) (OH) ].5(H O)} (3) and {[Zn(4ꢀbpdb)(fum)].(H O) (4). Here 3 shows a
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}
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pillared layer structure and 4 is a fivefold interpenetrated dimondoid network. Now moving
to the use of a shorter length ligand straight linker; 1,2ꢀbis(4ꢀpyridyl)ethylene (bpee), along
with suc and fum produced two MOFs, {[Zn(bpee)(suc)]
.(H
2 2
O)
3
}
n
(5) and
{
[Zn (bpee) (fum) ].(H O)} (6), where similar structural difference like 3 and 4 has been
2
2
2
2
n
found. The 5 shows a pillarꢀlayer structure and fum containing 6 produced five fold
interpenetrated dimondoid network. All these observations are based upon the
characterization of the above compounds single crystal Xꢀray diffraction, powder Xꢀray
diffraction (PXRD), elemental analysis, infrared (IR) spectroscopy, UVꢀvis spectroscopy,
thermogravimetric (TG) analyses. The gas/solvent vapor sorption study has been performed
for all four 3D compounds (3ꢀ6). In case of 3 an interesting reversible crystalline to
crystalline transformation was observed which has been thoroughly investigated by PXRD
analysis, IR spectroscopy and UVꢀvis spectroscopy. Photoluminescence of all the compounds
along with their constituent ligands has also been studied.
EXPERIMENTAL SECTION
3 2 2
Materials Highly pure Zn(NO ) ꢁ6H O, 1,2ꢀbis(4ꢀpyridyl)ethylene (bpee), pyrideneꢀ4ꢀ
aldehyde and pyrideneꢀ3ꢀaldehyde were purchased from the SigmaꢀAldrich Chemical Co. All
other reagents and solvents were purchased from commercial sources and were used without
further purification. 1,4ꢀbis(3ꢀpyridyl)ꢀ2,3ꢀdiazaꢀ1,3ꢀbutadiene (3ꢀbpdb) and 1,4ꢀbis(4ꢀ
pyridyl)ꢀ2,3ꢀdiazaꢀ1,3ꢀbutadiene (4ꢀbpdb) were synthesized by typical condensation reaction
between pyrideneꢀ4ꢀaldehyde or pyrideneꢀ3ꢀaldehyde and hydrazine hydrate following the
45,36
reported procedure.
NaHCO
and was allowed to evaporate until dryness.
Physical Measurements Elemental analyses (carbon, hydrogen, and nitrogen) were
Na
2
ꢀsuc or Na
2
ꢀfum was synthesized by the slow addition of solid
3
to the corresponding acid (H
2
ꢀsuc and H ꢀfum respectively) in water in a 2:1 ratio
2
−1
performed using a Heraeus CHNS elemental analyzer. Infrared spectra (4000–400 cm ) were
taken on KBr pellet, using Perkin–Elmer Spectrum BXꢀII IR spectrometer. Thermal analysis
(TGA) was carried out on a METTLER TOLEDO TGA 850 thermal analyzer under nitrogen
3
ꢀ1
atmosphere (flow rate: 30 cm min ) at the temperature range 30ꢀ600º C with a heating rate
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of 2º C/min. Xꢀray powder diffraction (PXRD) patterns in different states of the samples were
recorded on a Bruker D8 Discover instrument using CuꢀKα radiation (λ = 1.5406 Å),
operating at 40 kV and 40 mA. Absorption spectra of the solid samples were collected in
Perkin–Elmer Lamdaꢀ35 instrument with integrating sphere arrangement. Fluorescence
measurements were done using Horiba FluoroMax 4.
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Synthesis of {[Zn(suc)(3ꢀbpdb)].(H
An aqueous solution (4 ml) of disodium salt of succinic acid (Na
was mixed slowly with a methanolic solution (4 ml) of 3ꢀbpdb (0.25 mmol, 53 mg) and
stirred for 30 min to prepare the mixꢀligand solution. Zn(NO ·6H O (0.25 mmol, 75 mg)
2 2 n
O) } (1).
2
ꢀsuc) (0.25 mmol, 41 mg)
3
)
2
2
was dissolved in 4 mL water and then in a long crystal tube 4 ml of Zn(II) solution was
slowly and cautiously layered with the 8 ml of aforesaid mixedꢀligand solution, separated by
2
mL of a 1:1 waterꢀmethanol buffer. Yellowꢀcolored needleꢀshaped single crystals suitable
for Xꢀray diffraction analysis were obtained from the junction of the layer after one week.
The crystals were separated and washed with copious amounts of cold 1:1 (v/v) water and
methanol, and dried under air (yield = 71% based on Zn). Anal. Cal. for C16
18 4 6
H N O Zn
(427.73), 1 : C, 44.93; H, 4.24; N, 13.10. Found: C, 44.81; H, 4.42; N, 13.29. IR spectra (KBr
−
1
pellet, 4000–400 cm ): 3138 (m), 1632 (s), 1599 (s), 1551 (m), 1468 (s), 1430 (s), 1397 (m),
313 (s), 1238 (s), 1190 (s), 1162 (m), 1126 (s), 1051 (s), 1027 (m), 974 (m), 946 (m), 874
(m), 812 (m), 701 (m), 661 (m), 641 (m), 407 (s).
Synthesis of {[Zn(fum)(3ꢀbpdb)(H O) ]} (2).
1
2
2
n
Compound 2 has been synthesized using the same procedure as that of 1, using disodium salt
of fumaric acid (Na ꢀfum) (1 mmol, 160 mg) instead of disodium salt of succinic acid (Na ꢀ
2
2
suc). After 14 days, needle shaped yellow crystals were obtained from the middle of the tube
and were separated and washed with methanol (yield = 67% based on Zn). Anal. Cal. for
16 16 4 6
C H N O Zn (625.71), 2 : C, 45.14; H, 3.79; N, 13.16. Found: C, 45.02; H, 3.88; N, 13.37.
−
1
IR spectra (KBr pellet, 4000–400 cm ): 3180 (b), 1632 (s), 1599 (s), 1580 (m), 1555 (s),
467 (s), 1431 (s), 1385 (s), 1313 (s), 1206 (m), 1189 (m),1126 (m), 1052 (s), 1028 (s), 970
(s), 944 (s), 875 (s), 803 (s), 699 (s), 680 (s), 642(s), 592 (s), 405 (s).
Synthesis of {[Zn (4ꢀbpdb) (suc) (OH) ]·5H O} (3).
1
4
2
3
2
2
n
Compound 3 has been synthesized by the same procedure as that of 1 using 4ꢀbpdb (1 mmol,
210 mg) instead of 3ꢀbpdb. Unlike the compounds, here the yellow colored block crystals
were obtained after a longer time. After seven weeks the crystals were obtained from the
middle of the tube and were separated and washed with methanol (yield = 69% based on Zn).
44 8 4
Anal. Cal. for C36H N O19Zn (1154.33), 3 : C, 37.46; H, 3.84; N, 9.71. Found: C, 36.99; H,
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−
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4.11; N, 9.33. IR spectra (KBr pellet, 4000–400 cm ): 3377 (b), 3260 (b), 2985 (m), 1613
m), 1570 (s), 1434 (s), 1416 (m), 1383 (s), 1308 (s), 1292 (s), 1226 (m), 1170 (m), 1068 (s),
027 (m), 960 (m), 880 (s), 814 (m), 691 (s), 670 (m), 532 (m), 505 (m).
Synthesis of {[Zn(fum)(4ꢀbpdb)].(H O) } (4).
(
1
2
2 n
Compound 4 has been synthesized adopting the same procedure as that of 1, using disodium
salt of fumaric acid (Na ꢀfum) (1 mmol, 160 mg) instead of disodium salt of succinic acid
(Na ꢀsuc) and 4ꢀbpdb (1 mmol, 210 mg) instead of 3ꢀbpdb . After 7 days, yellow needle alike
crystals were obtained from the middle of the tube and were separated and washed with
methanol (yield = 76% based on Zn). Anal. Cal. for C16 Zn (625.72), 4 : C, 45.14; H,
3.79; N, 13.16. Found: C, 45.37; H, 3.63; N, 13.29. IR spectra (KBr pellet, 4000–400 cm ):
435 (b), 1616 (s), 1596 (s), 1428 (s), 1366 (s), 1335 (m), 1228 (m), 1192 (m), 1063 (s), 1029
s), 957 (m), 823 (s), 799 (s), 693 (s), 517 (s), 427 (s).
Synthesis of {[Zn(suc)(bpe)] .(H O) (5).
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0
2
2
16 4 6
H N O
−
1
3
(
2
2
3 n
}
Compound 5 has been synthesized using the same procedure as that of 1, using 1,2ꢀbis(4ꢀ
pyridyl)ethylene (bpee) (1 mmol, 182 mg) instead of 3ꢀbpdb. After 14 days, white block
crystals were obtained from the middle of the tube and were separated and washed with 1:1
methanol/water (yield = 76% based on Zn).
Elemental analysis calculated for
32 34 4 2
C H N O11Zn
(781.36), 5: C, 49.19; H, 4.39; N, 7.17. Found: C, 49.36%; H, 4.27%; N,
−
1
7.32%. IR spectra (KBr pellet, 4000–400 cm ): 3391 (b), 1613 (s), 1506 (s), 1432 (s), 1402
m), 1292 (s), 1253 (s), 1221 (s), 1206 (s), 1189 (s), 1153(m), 1070 (s), 1028 (s), 984 (m),
79 (m), 840 (s), 629 (m), 568 (m), 553 (m).
Synthesis of {[Zn (fum) (bpee) ].(H O)} (6).
(
8
2
2
2
2
n
Compound 6 has also been synthesized using the same procedure as that of 1, using 1,2ꢀ
bis(4ꢀpyridyl)ethene (bpee) (1 mmol, 182 mg) instead of 3ꢀbpdb and disodium salt of fumaric
acid (Na
0 days, white block shaped crystals were obtained from the middle of the tube and were
separated and washed with 1:1 methanol/ H O (yield = 65% based on Zn). Anal. Cal. for
Zn (741.35), 6 : C, 51.84; H, 3.53; N, 7.56. Found: C, 51.63; H, 3.68; N, 7.37.
IR spectra (KBr pellet, 4000–400 cm ): 3550 (b), 3055 (m), 1614 (m), 1593 (m), 1432 (m),
3798 (m), 1254 (s), 1208 (s), 1187 (s), 1068 (s), 1026 (s), 981 (m), 841 (s), 798 (s), 695 (s),
552 (m).
The bulk compounds of 1ꢀ6 have been synthesized in powder form by the direct
2 2
ꢀfum) (1 mmol, 160 mg) instead of disodium salt of succinic acid (Na ꢀsuc). After
1
2
C
32
H
26
N
4
O
9
2
−1
1
mixing of the corresponding solution of ligands and metal salt in water at their equal molar
ratio. For all the compounds a precipitate appeared within 10 minutes of mixing and the
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solution is then stirred further for three hours; except the 3. For compound 3 the stirring is
continued for overnight. The compounds were separated by filtration and it is washed with
small amount of 1:1 (v/v) methanol/water and dried in air. Compounds purity was verified by
PXRD, which give good correspondence between simulated and bulkꢀphase PXRD. The
purity of the bulk sample was further confirmed by the results of elemental analysis and IR
spectra as well, which is also found in accordance with the data obtained for the single
crystals.
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SingleꢀCrystal Structure Analysis The single crystals of compounds 1ꢀ6 were mounted on
thin glass fibers with commercially available super glue. single crystal Xꢀray data collection
of all of these six crystals were collected at room temperature using Bruker APEX II
diffractometer, equipped with a normal focus, sealed tube Xꢀray source with graphite
46
monochromated MoꢀKα radiation (λ= 0.71073Å). The data were integrated using SAINT
47
program and the absorption corrections were made with SADABS. All six structures were
4
8
solved by SHELXS 2014 using Patterson method and followed by successive Fourier and
2
difference Fourier synthesis. Full matrix leastꢀsquares refinements were performed on F
48
using SHELXLꢀ2014 with anisotropic displacement parameters for all nonꢀhydrogen atoms.
4
8
Potential solvent accessible area or void space was calculated using PLATON multipurpose
crystallographic software. All the hydrogen atoms were fixed geometrically by HFIX
command and placed in ideal positions in case of all structures. Calculations were carried out
48
48
49
50
using SHELXL 2014, SHELXS 2014, PLATON v1.15, ORTEPꢀ3v2, WinGX system
51
52,53
Verꢀ1.80 and TOPOS.
Data collection and structure refinement parameters along with
crystallographic data for 1ꢀ6 are given in Table 1.
Sorption Measurements
Ambient pressure volumetric N
desolvated samples of 3 (3′), 4, 5 and 6, maintained by a liquidꢀnitrogen bath, in the relative
pressures ranging from 0 to 1 using a Quantachrome AutosorbꢀiQ adsorption instrument. CO
2
gas adsorption study was carried out at 77 K with the
2
sorption measurements were also performed at 195 K (dry iceꢀacetone cold bath) with same
pressure range and on same instrument. High purity gases were used for the adsorption
measurements (nitrogen, 99.999%; carbon dioxide, 99.95%). For water vapor sorption
measurement, experiment was performed at 298 K in the pressure range 0 to 0.9 with the
same instrument. Extent of adsorption was determined by monitoring the change in pressure
at the equilibrium state of the sample tube containing adsorbates. All operations were
computerꢀcontrolled and automatic.
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1
1
1
1
1
1
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1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
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3
3
3
3
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5
5
5
6
Tables
Table 1. Crystallographic and Structural Refinement Parameters for 1ꢀ6
1
2
3
4
5
6
formula
C
16
H
18
N
4
O
6
Zn
C
16
H
16
N
4
O
6
Zn
C
36
H
44
N
8
O19Zn
4
C
16
H
16
N
4
O
6
Zn
C
32
H
34
N
4
O11Zn
C
32
H
26
N
4 9 2
O Zn
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
formula
weight
crystal
system
space
4
27.73
425.72
monoclinic
P2 /n
1154.33
425.71
781.413
741.35
triclinic
Pī
monoclinic
P2 /n
mriclinic
monoclinic
orthorhombic
1
1
Pī
C2/c
Fdd2
group
a/ Å
a/Å
9.0977(2)
8.9913(2)
9.0519(7)
9.0401(7)
8.6199(9)
25.540(5)
5.831(5)
37.910(3)
8.2837(5)
11.3553(2)
11.4115(2)
10.1025(10)
c/ Å
α/°
11.2330(2)
90
11.1496(8)
90
14.4797(15)
81.768(7)
82.393(6)
15.508(5)
90
21.1744(15)
13.1231(2)
104.149(1)
99.867(1)
90
90
β/°
105.660(1)
105.451(5)
118.202(5)
γ/°
V/ Å3
Z
90
90
87.194(7)
1236.4(2)
90
90
100.074(1)
1582.14(5)
884.75(3)
879.40(12)
2035.3(19)
6649.5(8)
2
2
1
2
8
2
–
3
D / g cm
1.606
1.431
440
1.608
1.439
436
1.537
1.994
578
1.376
1.243
856
1.549
1.509
3168
1.552
1.577
752
c
–1
ꢂ /mm
F(000)
θ range/°
2.6ꢀ27.5
2.6ꢀ27.6
1.4ꢀ27.8
1.8ꢀ27.5
2.1ꢀ27.8
1.6ꢀ27.5
reflections
collected
unique
reflections
reflections
I > 2σ(I)
1
3680
14654
2022
18786
5635
15091
2345
26012
3898
26875
7232
2
036
1582
1336
3122
2122
3562
5704
Rint
0.043
0.088
1.05
0.070
0.97
0.022
1.02
0.055
1.05
0.033
1.05
goodnessꢀ
ofꢀfit (F )
1
.03
0.0299
.0690
R = ΣFo
2
R1 (I >
0.0495
0.1387
0.0819
0.0548
0.0337
0.0890
0.0341
0.0854
a
2
σ(I))
wR2(I >
0
0.2602
0.1740
a
2σ(I))
a
2
2
2
2 2 ½
–
F 
/
ΣFo, wR = [
Σ
(w
(Fo
–
Fc ) )/ Σw
(
Fo ) ] .
1
c
2
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RESULTS AND DISCUSSION
Synthesis
At room temperature Zn(II) along with salt of two dicarboxylic acids and three different
N,N′ꢀdonor linkers, 3ꢀbpdb (1 and 2), 4ꢀbpdb (3 and 4), and bpee (5 and 6) in
methanol/water medium are used for synthesis of all the compounds 1−6 employing slow
diffusion technique (Scheme 1).
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Structural
description
of
{[Zn(3ꢀbpdb)(suc)(H
2
O)
2
]}
n
(1)
and
{[Zn(3ꢀ
bpdb)(fum)(H
2
O) ]} (2). Singleꢀcrystal Xꢀray structural analysis revealed that compounds 1
2
n
and 2 are isostructural having monoclinic P2 /n space group with only difference in the
1
nature of dicarboxylate linkers (succinate in 1 and fumarate in 2). Both the compounds show
the formation of a twoꢀdimensional (2D) structure of Zn (II) ions linked by 3ꢀbpdb linker and
bridging succinate in the case of 1 and fumarate in the case of 2. Here, in both cases Zn(II)
center is located in a special position (1, 0, 1) and the asymmetric unit contains half of Zn(II)
along with half 3ꢀbpdb linker, half dicarboxylate ligand and one coordinated water molecule.
Here, each hexaꢀcoordinated Zn(II) centers with ZnN
2
O
4
binding set displays a distorted
a
octahedral geometry created by two carboxylate O atoms (O1 and O1 ) from two different
dicarboxylate (suc in 1 and fum in 2), two symmetry generated coordinated water molecules
a
a
(O1W and O1W ) and two 3ꢀpyridyl nitrogen atoms (N1 and N1 ) from two 3ꢀbpdb linkers
(Figure 1a for 1 and Figure 1b for 2).
Figure 1. View of the coordination environment around Zn(II): (a) for compound 1, (b) for
compound 2; Zn (green), N (blue), O (red), C (gray). (Symmetry code a = 2ꢀx, ꢀy, 2ꢀz.)
In 1 and 2, Zn–O bond lengths vary from 2.0522(14)–2.0985(15) Å and 2.056(3)–2.095(3)
Å, respectively, and the corresponding Zn–N bond lengths are 2.2093(18) (Table S1) and
2.200(4) (Table S2) for 1 and 2, respectively. The selected bond lengths and bond angles are
reported in Table S1 for 1 and Table S2 for 2. Here, each dicarboxylate ligand binds in a
bridging monodentate fashion in between two Zn(II) centers resulting the formation of a 1D
metal carboxylate chain (Figure S2a for 1 and Figure S2b for 2). The 1D metalꢀcarboxylate
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1
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1
1
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2
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2
2
2
2
2
2
3
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3
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5
5
5
5
5
5
5
5
6
chains are joined by the 3ꢀbpdb linkers to form a 2D arrangement in the crystallographic ab
plane (Figure 2a for 1 and Figure 2b for 2).
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
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0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 2. Twoꢀdimensional sheet structure viewed along c axis: (a) for compound 1, (b) for
compound 2. Schematic view of the 4ꢀConnected 2D net: (c) for compound 1, (d) for
compound 2.
5
2,53
The TOPOS
analysis reveals that both the structures can be represented as a 4ꢀconnected
4
2
uninodal net (Figure 2c for 1 and Figure 2d for 2) with point symbol {4 .6 }. In the crystal
packing, the coordinated water are attached with the free carboxylate oxygen atoms by means
of Hꢀbonding forming a supramolecular 3D structure in the crystallographic ac plane for both
of them (Table S3 for 1 and Table S4 for 2; Figure 3 for 1 and Figure S3 for 2).
Figure 3. (a) 1D metal carboxylate chains stitched by lattice water molecules in 1. (b)
Supramolecular 3D arrangement in 1 (H bonding: cyan dotted lines).
It is worth to mention that although there is some rigidity in the fum relative to the suc, the
positional effect and the bent nature of the 3ꢀbpdb linker circumvent the effect of the double
bond present in the fumarate, resulting similar bonding nature and net topology.
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Structural description of {[Zn
4
(4ꢀbpdb)
2
(suc)
3
(OH)
2
]·5H
2
O}
n
(3) and {[Zn(4ꢀ
bpdb)(fum)].(H O) (4)
2
2 n
}
Taking a straight chain linker 4ꢀbpdb instead of bent angular linker 3ꢀbpdb, there is a change
in binding mode as well as an enhancement of the flexibility of the N,N′ꢀdonor linker occurs
which exerts a marked effect on the overall structure of the MOFs. This features, probably,
acting for the rising of dimensionality for both the structures obtained with 4ꢀbpdb. Single
crystal Xꢀray structure determination of compound 3 reveals that it is a threeꢀdimensional
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(3D) network made up of Zn(II), suc dianion and 4ꢀbpdb spacer and the crystal belongs to
the triclinic Pī space group. In the asymmetric unit, there are two crystallographic
independent Zn(II) ions (Zn1 and Zn2), one 4ꢀbpdb linker, one and half of suc and a bridging
OH group. Two Zn(II) centers are in two different geometrical arrangements. The hexaꢀ
coordinated Zn1 centers are in a distorted octahedral geometry with ZnO N binding set and
5
1
the coordination is provided by one 4ꢀpyridyl nitrogen (N1) of 4ꢀbpdb spacer, three
b
carboxylate oxygen (O3, O4 and O6) atoms from three different suc ligands and two oxygen
c
of bridging hydroxyl group (O1 and O1 ) (Figure 4a). Every hydroxyl groups farther connect
Figure 4. (a) Coordination environment around Zn(II) ions in 3; Zn (green), N (blue), O
(red), C (gray). (b) 2D sheet constructed by the Zn(II) and succinate dianion. (c) Threeꢀ
dimensional (3D) structure in 3 with water filled 1D channels. (d) Schematic view of the 4ꢀ
connected 3D network of 3. (Symmetry code: a =1+x,1+y,ꢀ1+z; b=1ꢀx,1ꢀy,ꢀz; c =2ꢀx,1ꢀy,ꢀz.)
3 1
one more Zn1 and a tetrahedral Zn2 centre. The fourꢀcoordinated Zn2 is with a ZnO N
binding set which is satisfied by the hydroxyl group, two carboxylate oxygen atoms (O2 and
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1
1
1
1
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1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
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4
4
4
4
4
4
4
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5
5
5
5
5
5
5
5
6
b
a
O5 ) from two bridging suc ligands and one 4ꢀpyridyl nitrogen (N4 ) atom of 4ꢀbpdb (Figure
a). The details of Zn−O and Zn−N bond lengths are depicted in Table S5. Among them, the
4
Zn1−O bond length are in the range of 2.048(5) − 2.218(6)Å and Zn1−N bond lengths are
2.136(6) Å. However, the Zn2−O bond lengths lies in the range of 1.912(5) − 1.980(5) Å, and
Zn2−N the bond lengths are 2.031(6) Å. Thus two set of Zn
the help of hydroxyl group, forms the secondary building unit (Figure S4) having the unit
formula Zn 12. Two such units are connected by bridging suc and extend the structure
2
(Zn1 and Zn2), connected with
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
4
4
N O
along crystallographic a axis. A set of two connected suc farther, bonded to two Zn1 atoms of
two different SBU and extend the structure to a Znꢀsuc sheet in ab direction (Figure 4b).
Such sheets are farther linked up by 4ꢀbpdb linkers along c axis to form the ultimate 3D
structure (Figure 4c). Beyond that, the structure is further stabilized by the intermolecular πꢀπ
interaction (Figure S5) and details about that is presented in the Table S6. From the
5
2,53
topological analysis by TOPOS
it is revealed that this 3D structure can be represented as
4
4
2
5
5
5
6
biꢀnodal 5,7ꢀc net (Figure 4d) with the Schläfli symbol {3 .4 .5 }{3 .4 .5 .6 }. The distances
of two Zn1 through the twoꢀconnected suc is 8.99Å and Zn1ꢀZn2 through 4ꢀbpdb is 15.457Å.
These large distances eventually create quadrilateral pores along a direction which are
occupied by lattice water molecules (Figure 4c). On removal of the free water molecules, the
49
3
solventꢀaccessible void space of 3 calculated by PLATON is 286 Å which is about 23.1%
of the total unit cell volume.
Now, on introduction of double bond, in the dicarboxylate by use of more rigid fum
instead flexible suc along with 4ꢀbpdb and Zn(II) yielded yellow colored crystal of compound
4 having a fivefold interpenetrated diamondꢀtype framework, which crystalises in
monoclinic space group C2/c. Structural analysis illustrates that the asymmetric unit of 4
consists of one and half of Zn(II), fum, 4ꢀbpdb ligands and two oneꢀhalf of guest water
molecules (Figure 5a). Here, each Zn(II) center exhibits a four coordinated distorted
a
tetrahedral geometry with an N
2
O
2
donor set bonded to two oxygen atoms (O1, O1 ) from
a
two different fum ligands by monodentate bridging fashion and two nitrogen atoms (N1, N1 )
from two different 4ꢀbpdb linkers (Figure 5a). Here all the ZnꢀO and ZnꢀN bonds are
1
.946(3)Å and 2.041(3) respectively. All the bond distances and bond angles around Zn(II)
centers are presented in Table S7.
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Figure 5. (a) The coordination environment around Zn1 and Zn2 atoms in 4; Zn (green), N
(blue), O (red), C (gray). (b, c) Perspective view of a single diamondoid cage formed via
coordination of fum and bpee to Zn(II) centres in 4. (d) A single 3Dꢀdiamondoid network
showing large voids in 4. (e) Spaceꢀfilling model of the fiveꢀfold interpenetrated 3D
framework of 4. (f) Topological representation of the fiveꢀfold interpenetrating nets in 4 (five
different 3D nets are shown in five different colours). (Symmetry code: a = 2ꢀx,1+y,1/2ꢀz)
Each fum and 4ꢀbpdb bridges two Zn(II) centers and the arrangement finally leads to large
adamantaneꢀlike cages (Figure 5b). In such an adamantane cage, Zn⋯Zn distances through 4ꢀ
bpdb and fum are ~15.4 and ~8.8 Å, respectively. These adamantoid cages are interconnected
and extended to form 3D diamondoid network with large hexagonal channels of dimension
2
about 18.9×14.4 Å (Figure 5c). Topologically the framework can be presented as a 4ꢀ
6
connected uninodal net with the Schläfli symbol {6 }(Figure 5f). Every diamondoid 3D
networks are interpenetrated with another four equivalent diamondoid networks to form a
Class Ia fivefold interpenetrated dimondoid network (Figure 5eꢀf). Notably, the channels
dimention is sufficiently decreased and the overall a 1D rectangular channels of the
2
dimension 9.6×7.3 Å along b axis is outcome and guest water molecules are resides in these
49
channels (Figure 5d). By PLATON the solventꢀaccessible void space of 4 was calculated
and found as 27.5% of the total crystal volume.
Structural description of{[Zn (bpee) (suc) ].(H O) } (5) Compound 5 crystallizes in the
2
2
2
2
3 n
orthorhombic Fdd2 space group and the singleꢀcrystal Xꢀray structure analysis reveals the
formation of a three dimensional (3D) network structure with Zn(II) metal ions connected by
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1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
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4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
suc dianion and bpee linkers. The asymmetric unit of 5 contains one Zn(II) atom, one
bridging bpee ligand, one succinate and one and half latiice water molecules. As shown in
2 2
Figure 6a, each Zn(II) center with O N binding set is coordinated with two 4ꢀpyridyl
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 6. (a) Coordination environment around Zn(II) ions in 5, where Zn (green), N (blue),
O (red), C (gray); (b) View of [Zn(bpee)] twoꢀdimensional (2D) grid in 5; (c)Threeꢀ
n
dimensional (3D) structure in 5 with water filled 1D channels. (d) Schematic view of the 4ꢀ
connected 3D network of 5. (Symmetry code: a = ꢀ1/4+x,5/4ꢀy,ꢀ1/4+z; b = 3/4ꢀx,1/4+y,ꢀ
1/4+z).
b
nitrogen atoms (N1 and N2 ) from two different linear bpee linkers and two carboxylate
a
oxygen atoms (O1 and O3 ) from two different bridging succinate displaying a distorted
tetrahedral geometry. The ZnꢀO bond lengths lie in the range of 1.929(3) to 1.947(3) Å
whereas ZnꢀN bond lengths are 2.029(3)ꢀ2.066(2) Å (Table S8). Other bond lengths and
angles of Zn(II) coordination spheres are listed in Table S8. Here, each suc dianion binds two
Zn(II) centers in a bridging monodentate fashion to yield a undulating [Zn(suc)] chain
n
(
Figure S7a), which is further cross linked by bpee coꢀligands along two different directions
Figure 6b) to develop a 3D porous framework with the 1D channel along the
(
crystallographic bꢀaxis, which are occupied by lattice guest water molecules (Figure 6c). As
49
calculated by PLATON , without these lattice water molecules, the solventꢀaccessible void
space of 5 is found as 7.8% of the total crystal volume. The structure is farther stabilized by
5
2,53
the πꢀπ weak interaction (Figure S7b). Details are provided in the Table S9.The TOPOS
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analysis reveals that the structure can be represented as a 4ꢀconnected uninodal net (Figure
2
4
6
d) with Schläfli symbol for net {4 .8 }.
Structural description of {[Zn (bpee) (fum) ].(H O)} (6) Compound 6 crystallizes in the
2
2 2 2 n
triclinic Pī space group and the single crystal Xꢀray structure determination reveals a threeꢀ
dimensional (3D) fivefold interpenetrating diamondoid network made up of Zn(II), fum
dianion and bpee spacer. The asymmetric unit contains two crystallographically independent
Zn(II) ions (Zn1 and Zn2), one complete fum ligand, halves of two fum ligands with other
environment, one complete bpee linker, halves of two other bpee linkers and one guest water
molecule (Figure 7a). The pentaꢀcoordinated Zn1 center is in a distorted square pyramidal
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Figure 7. (a) The coordination environment around Zn1 and Zn2 atoms in 6; Zn (green), N
(blue), O (red), C (gray). (b) Perspective view of a single diamondoid cage formed via
coordination of fum and bpee to Zn(II) centres in 6. (c) A single 3Dꢀdiamondoid network
showing large voids in 6. (d) Spaceꢀfilling model of the fiveꢀfold interpenetrated 3D
framework of 6. (e) Topological representation of the fiveꢀfold interpenetrating nets in 6 (five
different 3D nets are shown in five different colours). (Symmetry code: a = 1+x, 1+y, 1+z)
54
geometry with 0.32 Addison parameter (tau) value and O N binding set satisfied by four
3
2
carboxylate oxygen (O3, O7 and O8) atoms from two bridging fum ligands and two 4ꢀpyridyl
nitrogen (N2 and N3) atoms from two different bpee spacers (Figure 7a). The hexaꢀ
coordinated Zn2 shows a distorted octahedral geometry with a O N binding set and the
4
2
coordination is provided by four carboxylate oxygen atoms (O1, O2, O5 and O6) from two
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bridging fum ligands and two 4ꢀpyridyl nitrogen (N1 and N4 ) atoms from two different bpee
spacers (Figure 7a). The Zn−O and Zn−N bond lengths and related angles for Zn1 and Zn2
centers are slightly different (Table S10). Among them, the Zn1−O and Zn1−N bond lengths
are in the range of 1.9524(17)−2.6041(19) Å and 2.0466(18)−2.0609(18) Å, respectively.
However, the Zn2−O bond lengths lies 2.116(2)−2.5352(19) Å, and Zn2−N the bond lengths
are 2.0468(18) and 2.0886(19) Å. Other bond lengths and angles within the coordination
spheres are listed in Table S10. Both the Zn(II) ions act as 4ꢀconnected nodes which are
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connected with each other by the fum and bpee linkers to generate a large adamantaneꢀlike
52,53
cages (Figure 7b and S8aꢀb). Topological analysis by TOPOS
reveals that the structure
can be represented as a 4ꢀconnected dia net topology (Figure 7c, 7e) with the Schläfli point
6
symbol {6 }. Due to the crystallographic difference between the fum dianion ligands, the
Zn···Zn distances through fum are 8.747, 8.902 and 9.148 Å; whereas, Zn···Zn distances
through the three crystallographically different bpee ligands are 13.377, 13.437 and 13.439
Å. These adamantoid cages are interlinked and extended to form 3D diamondoid network
2
with large hexagonal channels of about 16.7 × 19.4 Å (Figure 7dꢀe), which facilitate further
nucleation in the void spaces and allow the formation of equivalent diamondoid net in those
regions to generate a Class Ia fivefold interpenetrated dimondoid network (Figure 7dꢀe).
49
Calculation by PLATON suggests that this system contain 5.5% solvent accessible void of
total crystallographic volume without the lattice water molecules.
From the above discussion of all the structures it is evident that the ligands have
marked influence on the overall structure of the compounds. In case of 1 & 2, the ultimate
structure is influenced by the bent nature of the 3ꢀbpdb ligand, resulting same structure
thumping the effect rigid or flexible coꢀlinkers. On moving to straight coordinating N, N′
donor ligand, the enhancement in flexibility, may leads to the formation of the higher
dimensional structures. Structural similarity in 3 & 5 and 4 & 6 pairs suggests here the
overall structures is less directed by the N, N′ donor ligand in comparison to that of 1 & 2. As
described earlier in last two pairs both succinate containing 3 & 5 gives pillared layer 3D
structures whereas fumarate containing 4 & 6 forms Class Ia fivefold interpenetrated
structure. The rigidity of the fumarate is possibly responsible for the formation of rigid large
hexagonal channels which finally turns into the interpenetrated structures.
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Thermogravimetric Analysis (TG) and Powder Xꢀray Diffraction (PXRD) Study
To study the framework stability of the compounds 1ꢀ6, thermo gravimetric analyses (TGA)
and powder Xꢀray diffraction (PXRD) studies are carried out. For both the studies crystalline
powder sample is used and TGA have been carried out in the range of 25–650 °C (Figure
S9). Single crystal analysis has shown that isoꢀstructural compound 1 and 2 have no solvent
molecule and TGA is consistent with this and there is no significant weightꢀloss up to ~200
°C for both of them and then a steady decrease of weightꢀloss have been observed in the
TGA. Eventually, compound 3 shows a gradual weightꢀloss with a step of 7.66% (40–80 °C),
which corresponds to the escape of guest water molecules and the weight lose is equivalent to
~5 (4.88) water molecules. The desolvated framework is stable up to 150 °C and after that it
steadily disintegrates to unrecognized product. TGA curve (Figure S9) of the compound 4
shows there is no significant weight loss up to 90 °C and then it starts gradual weightꢀloss
with a step of 8.12% up to 190 °C, corresponds to ~2 water molecules. This dehydrated
framework is stable up to 270 °C. Afterwards it continuously dissociate to unidentified
product. The TG analysis of 5 depict that guest water molecules are started to escape just
after 40 °C and continuous up to 137 °C. A certain change in slope at ~137 °C temperature
indicate that guest molecules are completely removed from the system with ~7 % weight loss
which is equivalent to ~ 3 water molecules. Afterwards with almost same rate (but not equal)
it dissociates to unrecognized products. From TGA it has been revealed that compound 6
shows a sharp weightꢀloss with a step of 2.48 % (60–90 °C), corresponds to the escape of one
guest water molecules from the compound. This dehydrated framework is stable up to 370 °C
with no significant weight lose. This is followed by a sharp weight loss, caused by
unrecognized product probably due to the decomposition of the frameworks.
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For all the compound bulk phase purity is confirmed by the PXRD pattern of the simulated
and asꢀsynthesized data and it is clearly observable the bulk phase is good accordance with
the single crystal XRD data (Figure 8).
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Figure 8. Powder Xꢀray diffraction patterns of all the compounds (a) 1, (b) 2, (c) 3, (d) 4, (e)
5
and (f) 6.
Study of crystalline to crystalline transformation in 3
The PXRD pattern of desolvated phase of 3 (3′) displays shifting of a few peak positions
along with the appearance of some new peaks in comparison to the asꢀsynthesized pattern of
3
(Figure 9), signifying, rather than disintegration structural transformation after removal
coordinated molecules has taken place. Indexing of the PXRD data of 3′ (Figure S10) using
5
2, 53
TREOR program
implies a structural contraction along c axis by 23.48% (Table S11)
associated with the reduction of 21.11% in volume after the removal of the solvent
molecules.
Figure 9. Powder Xꢀray diffraction patterns of 3 in different state.
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On immersion of 3′ to water as well as waterꢀmethanol mixture, there is a formation of
compound, 3′′ which have PXRD pattern similar to that of the major peak found for the
simulated pattern of 3 (Figure 9). That is on rehydration of 3′ it again restored to its original
O
phase. There is an additional peak at 2θ = 7.2 for both the water as well as waterꢀmethanol
mixture immersed product, which is possibly due to unorganized crystal packing.
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This transformation is also monitored using IR and UVꢀvis spectroscopy. In IR spectroscopy
broadening of peak with shift in some peak is observed (Figure S11) which suggests there is a
change in coordination environment around metal centre. In UVꢀvis spectroscopy, there is a
~
20 nm shift in the maxima has been observed for the 3′ respect to the 3 of the peak at ~ 370
nm. The maximum at ~330 nm is totally absent in 3′ (Figure S12). Again on rehydration the
maxima position are restored as that of assynthesized (Figure S12). Thus the mentioned
transformation is reversible in respect of treatment with water and waterꢀmethanol mixture.
Among the structures reported here, only 3 and 6 consists of two crystallographically
II
independent metal (Zn ) centers whereas the others have only one independent metal centers
in their unit cell. Upon dehydration of 3 there may be a possibility of reorganization in the
structure through the flexible sucinate dianion linkage. This conversion may lead to form an
uniform Zn(II) centre in the transformed phase (3′) which is somehow supported by the
contraction of cell volume in the activated form of compound 3 (3′). But compound 6 being a
dense interpenetrated structure consisting of rigid fumarate, is not prone to show such
dynamicity; which has been observed in 3.
Adsorption Properties
As revealed from the single crystalꢀXRD structural analysis, 3, 4, 5 and 6 have water filled
cavities and the pore dimensions are comparable to the kinetic diameter of the gases and
solvent vapors of recent interest. Along with, except the 3, all other’s framework stability is
supported by TGA and PXRD measurements. As stated earlier, 3 undergoes a structural
transformation during the dehydration; although the transformed framework, 3′, is quiet
stable up to a certain high temperature. With all of the dehydrated frameworks sorption study
has been performed using different gases (N
98 K). All of these samples shows negligible amount of N
adsorption (Figure 10a).
2
at 77K and CO
2
at 195 K) and vapors (H
2
O at
2
2
uptake with a typeꢀII surface
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Figure 10. Sorption isotherms for (a) N
2 2 2
at 77 K; (b) CO at 195 K and (c) H O at 298 K, for
3′ (red), 4 (violet), 5 (black) and 6 (blue).
Similar phenomenon is observed for the CO
Figure 10b). Despite of large pore, low N uptake may be due to low thermal energy of N
77 K may not overcome the high diffusion barrier causing exclusion whereas for CO
blocking of the windows of unidirectional pore channels to the incoming larger sized CO
2
also; which also ends up with a very low uptake
(
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molecules may be the reason for such low uptake. Besides, although 3 has a very large pore,
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due to change of structure during the dehydration process by the pore volume is mostly
compromised resulting a low adsorption.
However, the water adsorption shows enhancement of amount of adsorption accompanied
2
with some interesting phenomenon. The H O adsorption profile for 3′, exhibits a gate
−1
opening phenomenon; no uptake (~5 mL g ) at low pressure and then at P/P
0
∼
0.422, a
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−1
sharp rise takes place upto P/P ∼ 0.599, associated with an uptake of amount of 207 mL g
0
−1
and the final uptake amount reaches to 235.6 mL g (Figure 10c). The final uptake amount is
equivalent to a total no of 12 water molecules i.e. the converted structure can uptake more
number of water molecules than the number present in its mother compound. For 4, a type II
−
1
adsorption is observed with a final uptake of ~69.3 mL g .There is a certain interesting
scenario with 5; it uptake water up to P/P ∼ 0.17 with a continuous rate of amount ~61 mL
0
−1
g , equivalent to 2.1 water molecule, then there is a change in rate of adsorption which ends
−
1
at P/P ∼0.35 an amount of ~85 mL g , equivalent to a total of three water molecules (Figure
0
−
1
1
0c). Again a change of rate is observed and final amount reaches ~150.3 mL g at P/P
0
∼
0
.90 which is equivalent to ~5 (5.2) molecule of water. No significant adsorption is observed
for 6; final amount is ~38.6 (Figure 10c).
This is clearly visible that all these metalꢀorganic frameworks with succinate linker
have greater affinity towards water relative to the coordination polymer containing fumarate
linker with identical coꢀligand. Although, double bond containing fumarate should have
greater tendency to adsorb polar water molecule but a lower adsorption is observed. This may
be corroborated to the fact that all the fumarate containing systems are interpenetrated in
nature which may block the pore window hence such lower adsorption is observed.
Luminescence Study
10
Optical properties of MOFs with d metal centres and recent successful use of them in
4
1,42
various applications,
have brought them one more time under the spotlight of interest of
1
0
researchers. Solid state photoluminescence study of the d complexes 1ꢀ6 and free respective
ligands here been performed at room temperature (Figure 11). The ligand 3ꢀbpdb and
corresponding complexes 1 and 2 show emission maxima at 398 nm (λex = 255 nm), 405 nm
(λex = 265 nm) and 408 nm (λex = 265 nm) respectively (Figure 11a). Similar emission
spectra is found for the 4ꢀbpdb and its complexes 3 and 4. Complexes 3 and 4 exhibit the
emission maxima at 396 nm (λ = 255 nm) and 407 nm (λ = 265 nm) respectively and the
ex
ex
ligand 4ꢀbpdb at 394 nm (λex = 250 nm) (Figure 11b). For the rest, ligand bpee shows
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emission spectra at 396 nm (λex = 260 nm) where its complex 5 and 6 shows emission
maxima at 401 nm (λex = 260 nm) and 396 nm (λex = 250 nm) respectively (Figure 11c).
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Figure 11. Emission spectra for complex 1ꢀ6 with constituent free N,N′ꢀdonor linker.
It is cleared from the emission spectrum of the three ligand and their complexes 1ꢀ6, exhibit
similar type of spectra with slightly red shifted compared to the ligand. The emission
spectrum of free ligands with aromatic architecture may be originated from the π*–n or π*–π
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transition. Since the d metal ions are difficult to be reduced or oxidized there is less
5
5
possibility to occur the metalꢀassociated MLCT/LMCT charge transfer. Thus, the emission
property of these compounds may be allocated primarily to the intra ligand charge transition
(ILCT) and ligandꢀtoꢀligand charge transfer (LLCT).
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CONCLUSION
Here syntheses of six Zn(II) MOFs constructed by succinate and fumarate along with three
different N,N′ donor coꢀligands, among them one is bent coordinating and other two are
straight coordinating. The ligand differs by chain length and constituent atoms as well. The
structural diversity was discussed and different physicochemical analysis has been performed
on them for proper characterization. It is also found that, one of the compounds, shows
reversible structural transformation on dehydration and rehydration which is also thoroughly
investigated by different techniques. Besides, results from the gas and solvent vapor sorption
experiments are found quiet interesting and consistent with the structural features. From the
study it is interesting to note that, despite of use of the both flexible and rigid dicarboxylate
linkers along with same bent coordinating ligand, 1 and 2 are found isostructural and rigidity
or flexibility of a ligand seems to have no effect on the overall structure. Although, the
compounds with straight coordinating linker have structural similarity as succinate containing
pair 3 & 5, and fumarate containing pair 4 & 6. The flexible succinate containing compounds
are portrayed pillared layer structure whereas fumarate containing compounds shows fivefold
interpenetrated structure. It has been quite ubiquitous that the pillared layer structure is more
likely to be formed by a rigid ligand and flexibility in ligand favors interpenetration, but here;
exactly opposite trend is observed. Another interesting phenomenon is worth to note, 3 & 5 is
made of succinate and linear flexible linker, but for 3 the flexibility is transferred to the
constructed MOF but 5 does not have any structural flexibility as found in 3. Also, 4 with
same N,N′ꢀdonor linker does not show any structural flexibility like 3. Therefore it is evident
from the present study that a rigid linker can able to create a flexible structure in a favorable
condition and vice versa.
ASSOCIATED CONTENT
Supporting Information
The figures related to IR, UVꢀVis spectral study; PXRD patterns, and TGA of compounds
along with different structural figures and tables related to the crystal structures reported in
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this paper are available as SI. CCDC 1572901ꢀ1572906 contains the supplementary
crystallographic data for this paper in CIF format.
AUTHOR INFORMATION
Corresponding Author
E–mail: dghoshal@chemistry.jdvu.ac.in, FAX: +9133 2414 6223
Notes: The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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DG gratefully acknowledges the financial assistance given by SERB (SB/S1/ICꢀ06/2014). FH
acknowledges UGC for the research fellowship.
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Table of Contents
Structural Diversity in Six Mixed Ligand Zn(II) MetalꢀOrganic
Frameworks Constructed by Rigid and Flexible Dicarboxylates and
Different N, N′ Donor Ligands
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Arijit Halder, Biswajit Bhattacharya, Fazle Haque and Debajyoti Ghoshal*
Study of the structure diversity for six functionalized metalꢀorganic frameworks of Zn(II),
synthesized using one rigid or flexible dicarboxylates along with three different N,N′ꢀdonor
ligand. Various physicochemical analyses suggest their properties are consistent with the
structural outcome.
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