Article

pubs.acs.org/crystal

Synthesis and Characterization of Polyhedral-Based MetalOrganic

Frameworks Using a Flexible Bipyrazole Ligand: Topological Analysis
and Sorption Property Studies
Kapil Tomar, Richa Rajak, Suresh Sanda, and Sanjit Konar*
Department of Chemistry, IISER Bhopal, Bhopal 462066, India
S Supporting Information
*

ABSTRACT: Six porous metalorganic frameworks (MOFs),

{[Ni(BTC)0.66(BPz)2]2MeOH4H2O}n (1), {[Co(BTC)0.66(BPz) 2 ]2MeOH4H 2 O} n (2), {[Mn(BTC) 0.66 (BPz) 2 ]
2MeOH4H2O}n (3), {[Cd(BDC)(BPz)(H2O)]2MeOH
DMF}n (4), {[Cd2(NH2-BDC)2(BPz)(H2O)]MeOHH2O
DMF}n (5), and {[Co(BDC)(BPz)(H2O)]}n (6) (where
H3BTC = 1,3,5-benzenetricarboxylic acid, H2BDC = 1,4benzenedicarboxylic acid, NH2-H2BDC = 2-amino-1,4-benzenedicarboxylic acid, and BPz = 3,3,5,5-tetramethyl-4,4bipyrazole), were obtained through a solvent diusion
technique and characterized. The networks exhibit a variety
of topologies: 1, 2, and 3 are isostructural and possess
octahedral and cuboctahedra type cages and exhibit 3,6-c
binodal net having loh1 topology, 4 is a two-dimensional MOF having one-dimensional open channels with a 4-c uninodal net
having sql topology, 5 exhibits a three-dimensional (3D) porous MOF having a 3,3,4,8-c net with a new topology having the
name, skr1, whereas 6 discloses a 3D nonporous network which exhibits a 4-c uninodal net having CdSO4 topology. Being
isostructural, gas sorption studies of 13 show nearly the same CO2 sorption at 195 K of 90 mL g1, whereas 4 and 5 show a
maximum uptake of 42 and 37 mL g1 at 195 K. Vapor sorption studies of 13 reveal stepwise uptake of water with a nal
amount reached to nearly 350 mL g1, whereas 4 and 5 show maximum uptake of 110 and 90 mL g1, respectively. Compared to
the free ligand BPz, photoluminescence studies of 4 and 5 show red shifts and emit in the blue-green region with max at 430 and
472 nm for 4 and 5, respectively.

MOFs have been reported recently.4456 The advantage

associated with BPz-based MOFs is that they possesses
considerable exibility due to the free rotation of CC bond
between the pyrazole rings. This results in various possibilities
of coordination networks due to non-collinear orientation of
the two Nmetal bonds. Furthermore, BPz can act as a neutral
bridging ligand to ligate two metal ions, or it can act as a
monoanionic or dianionic linker to bridge more than two metal
ions. These features may result in a diverse range of
dimensionalities and topologies in BPz-based MOFs. Additionally, due to the robustness of the metalazole bonds, the azolebased MOFs display good thermal stability and resistance
toward water. Although with BPz many porous MOFs are
reported, this is the rst time where polyhedral-based porous
assemblies were obtained. Along with a substantial amount of
CO2 uptake, these MOFs showed unexpectedly high and
stepwise water sorption (350 mL g1). This high uptake of
water is contradicting the fact that the cages are decorated with
hydrophobic moieties (methyl groups of BPz).

n the past few decades, the design and synthesis of porous

metalorganic frameworks (MOFs) have attracted extensive
interest owing to their variety of architectures and intriguing
topologies19 as well as potential applications.1021 Especially
the supramolecular assemblies of discrete cages and cagelike
polyhedral-based MOFs have become a topic of interest as they
are dierent from typical MOFs having open channel type
pores, whereas polyhedral-based MOFs consist of individual
cages carrying large voids which are connected through small
windows.2234 These features make polyhedral-based MOFs
more useful in storage of small molecules.35 The potential use
of such compounds largely depends on their cavity shape and
size, which are largely controlled by the type of organic ligand
used in the construction. These cage-based MOFs have been
prepared mostly by rigid linkers, whereas exible or semirigid
linkers have been rarely used.36,37 It is a well-established fact
that network topologies are greatly inuenced by linker
molecules. Especially, in the case of exible spacers, new
topologies can be discovered as the changeable conformation
and exibility may lead to richness and unpredictability of the
formed MOF structures.3843
In the category of semirigid ligand, 3,3,5,5-tetramethyl-4,4bipyrazole (BPz) is a well-known linker with which several
XXXX American Chemical Society

Received: January 14, 2015

Revised: March 16, 2015

DOI: 10.1021/acs.cgd.5b00056
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solvent vapor adsorption studies were performed using BELSORP

MAX and BELSORP AQUA (BEL JAPAN) volumetric adsorption
analyzer.
Crystal Data Collection and Structure Determination.
Suitable single crystals of each of the complexes were mounted on a
Bruker SMART II diractometer equipped with a graphite
monochromator and MoK ( = 0.71073 , 140 K) radiation.
Data collection was performed using a and scan. The structures
were solved using direct methods followed by full matrix least-squares
renements against F2 (all data HKLF 4 format) using SHELXTL.
Subsequent dierence Fourier synthesis and least-squares renement
revealed the positions of the remaining non-hydrogen atoms.
Determinations of the crystal system, orientation matrix, and cell
dimensions were performed according to the established procedures.
Non-hydrogen atoms were rened with hydrogen atoms placed
geometrically and rened using the riding model. All calculations were
carried out using SHELXL 97,58 PLATON 99,59 and SHELXTL60
program packages. The solvent molecules in 15 are highly
disordered. Therefore, the SQUEEZE61 program was used, and a
new .HKL le was generated. The structures were solved by using the
newly generated .HKL le. Structure renement after modication of
the data with the SQUEEZE led to better renement and data
convergence. Detail instruction from the .SQF le is included in the
nal cif le. The solvents molecules were calculated on the basis of a
combined study of TGA, elemental analysis, and removed electron
counts which are included in the molecular formula. Data collection
and structure renement parameters and crystallographic data for the
six complexes are given in Table 1.
Synthesis of {[Ni(BTC)0.66(BPz)2]2MeOH4H2O}n (1). The
sodium salt of H3BTC (0.2 mmol, 46 mg), Ni(NO3)26H2O (0.2
mmol, 60 mg), and BPz (0.3 mmol, 57.6 mg) were dissolved
separately in 12 mL of water and 15 mL of methanol solution,
respectively. Two milliliters of the metal and BPz solution was slowly
and carefully layered above 2 mL of Na3+BTC3 solution in a narrow
glass tube using 1 mL of buer (1:1 H2O and MeOH) solution. Light
green, block-shaped single crystals were obtained from the junction of
the layers after 1 week. The crystals were separated and washed with
MeOH and air-dried (yield: 55%). Elemental analysis: Anal. Calcd For
C28H48N8O10Ni (%): C, 47.01; H, 6.76; N, 15.66; Found (%): C,
47.45; H, 5.96; N, 16.04. FT-IR (KBr pellet, cm1): 3444 (b), 1622
(s), 1568 (s), 1400 (s), 1072 (m), 830 (w), 785 (w), 533 (w) (Figure
S1a, Supporting Information).

Herein, we report six MOFs out of which three are

isostructural polyhedral-based porous MOFs, namely, {[Ni(BTC) 0.66 (BPz) 2 ]2MeOH4H 2 O} n (1), {[Co(BTC) 0.66 (BPz)2]2MeOH4H2O}n (2), and {[Mn(BTC)0.66(BPz)2]
2MeOH4H2O}n (3). Also, we employed H2BDC/NH2H2BDC and BPz ligands with Co2+ and Cd2+ ions to produce
three new MOFs, namely, {[Cd(BDC)(BPz)(H2O)]2MeOH
DMF}n (4), {[Cd2(NH2-BDC)2(BPz)(H2O)]MeOHH2O
DMF}n (5), and {[Co(BDC)(BPz)(H2O)]}n (6) (where,
H3BTC = 1,3,5-benzenetricarboxylic acid, H2BDC = 1,4benzenedicarboxylic acid, NH2-H2BDC = 2-amino-1,4-benzenedicarboxylic acid) (Schemes 1 and 2).
Scheme 1. Schematic Drawing of the Ligands

EXPERIMENTAL SECTION

Materials and General Procedure. All the reagents and solvents

were procured from S. D. Fine Chemicals, India. BPz was synthesized
according to a literature method.57 H3BTC, H2BDC, and NH2H2BDC were obtained from the Sigma-Aldrich Chemical Co. and used
as received.
The elemental analysis was carried out on Elementar Micro vario
Cube elemental analyzer. The IR spectrum of the compounds 16
were recorded on a PerkinElmer FT-IR Spectrum BX using the KBr
pellets in the region of 4000400 cm1. Thermogravimetric analysis
(TGA) was carried out (PerkinElmer) in the temperature range of
30700 C (heating rate 5 C min1). Powder X-ray diraction
(PXRD) data were collected on a PANalytical EMPYREAN
instrument using CuK radiation.
Sorption Studies. In order to evaluate the porous property of all
the complexes, the crystalline materials are ground to powder and
activated by drying under a vacuum at 100 C for 10 h. Gas and

Scheme 2. Synthetic Scheme of 16

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Table 1. Crystal Data and Structure Renement for 16

empirical formula
formula weight
crystal system
space group
a ()
b ()
c ()
(deg)
(deg)
(deg)
V (3)
Z
temperature (K)
range
goodness-of-t
R1a
wR2b
F(000)
a

C26H30NiN8O4
577.27
trigonal
R3c
19.688(15)
19.688(15)
48.637(5)
90
90
120
16327(2)
18
140(2)
2.0028.21
1.155
0.065
0.132
5436.0

C26H30CoN8O4
577.51
trigonal
R3c
19.791(6)
19.791(6)
48.771(15)
90
90
120
16544(9)
18
140(2)
2.4727.92
0.999
0.066
0.173
5418.0

C26H30MnN8O4
573.52
trigonal
R3c
19.935(6)
19.935(6)
50.377(13)
90
90
120
17339.0(9)
18
140(2)
2.2827.67
1.168
0.068
0.152
5382.0

C18H20CdN4O5
484.79
monoclinic
P21/n
10.340(5)
12.798(5)
19.845(5)
90
99.722 (5)
90
2588.4(17)
4
140(2)
2.3427.47
0.989
0.050
0.126
976.0

C26H26Cd2N6O9
791.35
monoclinic
P21/n
16.224(5)
12.979(4)
16.226(5)
90
100.056 (10)
90
3364.1(17)
4
140(2)
2.2427.12
0.996
0.080
0.194
1568.0

C18H20CoN4O5
431.31
monoclinic
P21/n
11.218(9)
17.326(10)
11.235(8)
90
116.602 (5)
90
1952.7(2)
4
140(2)
2.3727.38
0.827
0.052
0.105
892.0

R1 = Fo| |Fc/|Fo. bR2 = [{w(Fo2 Fc2)2}/{w(Fo2)2}]1/2.

Figure 1. (ac) Coordination environments of Ni2+, Co2+, and Mn2+ in 13. (d) A view of the octahedral and cuboctahedral in 1. (e) 3D packing
view of 1 along the c-axis. (f) NHO (NO = 2.672(3) ) type hydrogen bonding in 1. (g) Schematic diagram depicting the connectivity of two
polyhedral in 13. (h) Connolly surface in 1 showing the solvent accessible void volume. (i) Topology of 13, showing the 6,3 connected nodes.
C

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Synthesis of {[Co(BTC)0.66(BPz)2]2MeOH4H2O}n (2). The same

diusion technique of 1 was employed for the synthesis of compound
2 using Co(NO3)26H2O (0.2 mmol, 58.2 mg), BPz (0.3 mmol, 57.6
mg) and sodium salt of H3BTC (0.2 mmol, 46 mg). Purple-colored
crystals were obtained after 1 week. The crystals were separated and
washed with MeOH and air-dried (yield: 59%). Elemental analysis:
Anal. Calcd For C28H48N8O10Co (%): C, 46.99; H, 6.76; N, 15.66;
Found (%): C, 46.32; H, 5.78; N, 15.14; FT-IR (KBr pellet, cm1):
3428 (b), 1627 (s), 1420 (s), 1386 (s),1308 (w), 1233 (m), 1191 (s),
1116 (b), 1028 (m), 958 (m), 798 (s), 697 (s) (Figure S1b,
Supporting Information).
Synthesis of {[Mn(BTC)0.66(BPz)2]2MeOH4H2O}n (3). The
same diusion technique of 1 was employed for the synthesis of
compound 2 using MnCl24H2O (0.2 mmol, 39.58 mg), BPz (0.3
mmol, 57.6 mg), and sodium salt of H3BTC (0.2 mmol, 46 mg).
Colorless crystals were obtained after 12 days. The crystals were
separated and washed with MeOH and air-dried (yield: 50%).
Elemental analysis: Anal. Calcd For C28H48N8O10Mn (%): C, 47.26;
H, 6.80; N, 15.75; Found (%): C, 47.05; H, 6.16; N, 15.04; FT-IR
(KBr pellet, cm1): 3428 (b), 1626 (s), 1420 (s), 1386 (s),1308 (w),
1233 (m), 1191 (s), 1116 (b), 1028 (m), 958 (m), 798 (s), 697 (s)
(Figure S1c, Supporting Information).
Synthesis of {[Cd(BDC)(BPz)(H2O)]2MeOHDMF}n (4). The
same diusion technique of 1 was employed for the synthesis of
compound 4 using Cd(NO3)24H2O (0.2 mmol, 61.7 mg), BPz (0.3
mmol, 57.6 mg), and sodium salt of H2BDC (0.2 mmol, 33.23 mg).
Colorless crystals were obtained after 1 week. The crystals were
separated and washed with MeOH and air-dried (yield: 62%).
Elemental analysis: Anal. Cald. For C23H35CdN5O8. (%) C, 44.42; H,
5.67; N, 11.26; Found (%): C, 43.85; H, 5.23; N, 11.07; FT-IR (KBr
pellet, cm1): 3428 (b), 1629 (s), 1420 (s), 1386 (s),1308 (w), 1233
(m), 1191 (s), 1116 (b), 1028 (m), 958 (m), 798 (s), 697 (s) (Figure
S1d, Supporting Information).
Synthesis of {[Cd2(NH2-BDC)2(BPz)(H2O)]H2OMeOHDMF}n
(5). The same diusion technique of 1 was employed for the synthesis
of compound 5 using Cd(NO3)24H2O (0.2 mmol, 61.7 mg), BPz (0.3
mmol, 57.6 mg), and sodium salt of NH2-H2BDC (0.2 mmol, 36.23
mg). Colorless crystals were obtained after 1 week. The crystals were
separated and washed with MeOH and air-dried (yield: 65%)
Elemental analysis: Anal. Calcd For C30H39Cd2N7O12(%): C, 39.40;
H, 4.30; N, 10.72. Found (%): C, 39.05; H, 4.47; N, 11.07. FT-IR
(KBr pellet, cm1): 3413.04 (b), 3222.82 (b), 2929.34 (w), 1595.66
(b), 1415.95 (b), 1258.4 (w), 1187.77 (w) (Figure S1e, Supporting
Information).
Synthesis of {[Co(BDC)(BPz)(H2O)]}n (6). The same diusion
technique of 1 was employed for the synthesis of compound 6 using
Co(NO3)26H2O (0.2 mmol, 58.2 mg), BPz (0.3 mmol, 57.6 mg), and
sodium salt of H2BDC (0.2 mmol, 33.23 mg). Colorless crystals were
obtained after 1 week. The crystals were separated and washed with
MeOH and air-dried (yield: 60%). Elemental analysis: Anal. Calcd For
C18H20CoN4O5 (%): C, 50.12; H, 4.67; N, 12.99. Found (%): C,
49.58; H, 4.36; N, 12.35. FT-IR (KBr pellet, cm1): 3423.04 (b),
3226.82 (b), 2927.34 (w), 1581.66 (b), 1418.95 (b), 1261.4 (w),
1188.77 (w) (Figure S1f, Supporting Information).
The bulk amount of the compounds 16 were prepared in powder
form by the direct mixing of the ligands mixture with a corresponding
solution of metal salt followed by overnight stirring. All major peaks in
experimental PXRD of compounds 16 match well with simulated
PXRD, which indicates equitable crystalline phase purity (Figure S2,
Supporting Information).

ion is coordinated by four nitrogen atoms of four BPz

molecules and two oxygen atoms from two BTC3 molecules in
an NiN4O2 environment giving it a distorted octahedral
coordination geometry. The equatorial plane is formed by
four nitrogens, while the two oxygen atoms occupy the axial
positions with measured bond distances of NiN in the range
of 2.092(3)2.098(2) , while the NiO distance is 2.102(5)
. The ONiO angle is 173.77 (5). The interpyrazole
dihedral angle for the BPz ligand is 63.30(4) with exobidentate coordination mode. The BTC3 anion is in a (1-0)(1-0)-(1-0)-3 coordination mode (Scheme 3). This type of
Scheme 3. Various Bridging Modes of Ligands in 16

monodentate coordination mode of BTC3 ligand is rare in

MOFs and is observed only in a few compounds reported by
Mukherjee and Rosseinsky groups.6264 The free oxygen of the
-COOH group is engaged in hydrogen bonding with the -NH
moiety of the pyrazole ring (N2H2O2, N2O2, 2.672(3)
) (Figure 1f).
More insight into the structure revealed that [Ni-(BTC)0.66]n
is arranged into a 2D neutral (6,3) connected sheets with
hexagonal rings along the c-axis (Figure S3a, Supporting
Information). The second honeycomb sheet was stacked on
rst with an oset and was pillared by BPz molecules, which
ultimately resulted in a pillar-layered porous 3D MOF (Figure
S3b, Supporting Information). From a topological point of
view, the overall framework is made up of two types of
polyhedral cages, cuboctahedral and octahedral. The cuboctahedral cage is constructed from 12 Ni(II) ions, 12 BPz, and
eight BTC3 molecules. The cage consists of eight triangular
and six square faces and can enclose a sphere of diameter 6 .
The octahedral cage involves six Ni(II) ions, six BPz, and two
BTC3 molecules and can enclose a sphere of diameter 3
(Figure 1d). In the crystal, one cuboctahedral cage is joined to
six others by sharing a square window and to eight other
octahedral cages by sharing a triangular window to form a 3D
porous architecture (Figure 1e).
The formed voids in the two polyhedral cages are
interconnected through relatively narrow passages as the
triangular and square faces are eectively blocked by methyl
groups of the BPz molecules. This feature also prevents the
interpenetration of the framework and allows a substantial
amount of porosity. The total solvent-accessible volume for 1
was estimated to be 36.9% (6029.2 3 out of 16326.8 3) by

RESULTS AND DISCUSSION

Structural Description of Complexes 1, 2, and 3. Since
all three complexes are isostructural, the detailed structural
description of only complex 1 is discussed here. Complex 1
crystallizes in trigonal system and R3c space group. The
asymmetric unit contains one-half occupied Ni(II) ion, one BPz
ligand, and one-third of BTC3 molecule as well as some
disordered solvent molecules. As shown in Figure 1a, the Ni(II)
D

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Figure 2. (a) Coordination environment of Cd2+ in 4. (b) A square grid type 2D sheet in 4. (c) Stacking of 2D layers to form porous network in 4.
(d) OHO (OO = 2.738(8) ) type hydrogen bonding between 2D layers. (e) Connolly surface in 4 showing the pore shape. (f) 4 connected
sql topology in 4.

continuous 1D channel formation occurs along the b-axis with

rough dimensions of 8.88 6.78 (Figure 2c). In the 3D
packing, the sheets were held together by OHO (OO =
2.738(8) ) type hydrogen bonds between coordinated water
molecules and carboxylate groups of BDC2 molecules in the
adjacent sheets (Figure 2d). The channels are lled with
disordered solvent molecules which were removed by the
SQUEEZE command of PLATON. The total solvent accessible
void volume as estimated by PLATON is found to be 31.5%
(815.0 3 out of 2588.4 3).
The topological analysis reveals that the Cd(II) center acts as
a four-connected node, while the BDC2 and BPz ligands were
considered as simple linkers; therefore one 2D layer can be
envisioned as a 4-c uninodal net (Figure 2f). It has a Point
symbol of {44.62}, which is assigned to topology type sql/
Shubnikov tetragonal plane net (topos & RCSR.ttd).
Structural Description of Complex 5. The asymmetric
unit of 5 consists of two crystallographically independent
Cd(II) ions, two NH2BDC2 molecules, one bipyrazole, and
one coordinated water molecule along with disordered solvent
molecules in the lattice. The Cd1 and Cd2 acquire distorted
pentagonal bipyramidal geometry (Figure 3a). The Cd1 is
coordinated to four oxygen atoms of two BDC2, one oxygen
atom of water molecule, one nitrogen atom of the -NH2 group
of BDC2, and one nitrogen atom from BPz ligand. The Cd2 is
coordinated to ve oxygen atoms of three BDC2, one nitrogen
atom of -NH2, and one nitrogen atom of BPz ligand. In both
the metal centers nitrogen atoms are located at the axial
positions, while the oxygen atoms form the equatorial plane.
The middle of the two Cd2Cd2 centers is present on the
inversion center with a Cd2Cd2 distance of 3.881 . The
CdO bond distances for Cd1 are in the range 2.290 (3)
2.557 (6) , while for Cd2 the range is 2.316 (3)2.561 (4) .
The CdN distances for Cd1 and Cd2 are 2.316 (3) , 2.385
(5) and 2.316 (4) , 2.459 (6) , respectively. Both the
BDC2 molecules bind to the metal in a chelating mode

summing voxels more than 1.2 away from the framework

using PLATON software.
Topologically, each Ni(II) ion has been linked by six ligands;
therefore it can be simplied into a 6-connected node. The BPz
ligand can be omitted due to its linear geometry, and one
BTC3 molecule is connected to three Ni(II) molecules;
therefore it can be considered as a three connected node. The
whole network can thus be viewed as a 3,6-c binodal net
(Figure 1i) with stoichiometry (3-c)2(6-c)3. It has a Point
symbol of {43}2{46.66.83}3 which is assigned to topological type,
loh1 (personal.ttd).
Structural Description of Complex 4. The asymmetric
unit has one each of Cd(II), BPz, BDC2 and one coordinated
water molecule along with disordered solvent molecules. As
shown in Figure 2a, the Cd(II) ion is coordinated from four
oxygen atoms of BDC2, two nitrogen atoms of BPz, and an
oxygen atom of coordinated water in a CdO5N2 environment
giving it a distorted pentagonal bipyramidal geometry. The
nitrogen atoms occupy the axial positions, while the oxygen
atoms form the equatorial plane. The CdO bond distances fall
in the range 2.299(4)2.567(3) , while the CdN distances
are measured as 2.337(3) and 2.363(2) . The BDC2 anion is
in a chelating (1)-((1)-2 coordination mode. Similar to
complexes 13, here also, the -COOH group is engaged in
hydrogen bonding with the -NH moiety of the pyrazole ring.
The [Cd-BDC]n moiety forms innite parallel chains which
are connected to each other by BPz molecules to form a 2D
open gridlike undulated sheet structure which is shown in
Figure 2b. A similar type of 2D grid was also observed in the
Zn-BDC-BPz system reported by He et al.,65 but in 3D packing
the open pores vanished due to 2-fold interpenetration. Two
CdCd distances in the grid is measured as 10.340 (4) and
11.302 (3) . The dihedral angle between the pyrazole rings in
BPz is found to be 75.77 (4), which is quite higher than
complexes 13, having an exo-bidentate co-ordination mode.
The 2D sheets stack upon each other in such a way that a
E

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Figure 4. (a) Coordination environment of Co2+ in 6. (b) A portion of

the 2D sheet struture in 6. (c) 3D packing diagram of 6. (d) Figure
depicting the 4-connected CdSO4 topology of 6.

Figure 3. (a) Coordination environment of Cd2+ in 5. (b) 3D porous

framework along the b-axis (methyl groups of BPz have been omitted
for clarity). (c) 3,3,4,8-c net in 5 with a new topological type, skr1. (d)
Connolly surface in 5 showing the closed pores.

distances fall in the range 2.031(4)2.195(3) , while the

Co(II)N distances are found to be 2.137(2) and 2.151(4) .
The oxygen atoms from BDC2 form the equatorial plane,
while the nitrogen atoms from BPz occupy the axial positions
with a NCoN angle of 177.79 (5), which is very close to
the ideal angle of 180. The dihedral angle between the
pyrazole rings is measured to be 80.40, which is the highest
value among complexes 16 having endo-bidentate coordination mode. Out of two types of crystallographically
independent BDC2 molecules, one has monodentate, while
the other has a chelating mode of coordination with (1)-((1)2 coordination mode. These BDC2 molecules form a 1D
innite chain with Co(II) ion and are further connected by BPz
molecules to form a 3D network (Figure 4c). Although the
number and type of ligands coordinated in 6 is similar to 4, the
resulting geometries are dierent. In 4, both the -COOH
groups coordinated in chelating mode, while in 6 one of the
-COOH is showing monodentate mode (due to the high
coordination number of Cd2+ than Co2+). Along with this, one
more dierence is in the dihedral angles of the BPz ligand in
both complexes (75.77 in 4 and 80.40 in 6). These two
dierences gave entirely dierent structures with a 2D network
in 4 (sql topology) and 3D network in 6 (CdSO4 topology).
Topological analysis shows that Co(II) can be considered as
a 4-connected node (four ligands are connected to Co(II)),
whereas BDC2 and BPz are considered only as simple linkers;
therefore the whole network is classied as a 4-c uninodal net
with a Point symbol of {65.8} (Figure 4d). The assigned
topology is cds CdSO4; 4/6/t4; sqc5 (topos & RCSR.ttd).
PXRD and TGA Studies. To examine the thermal stability
and phase purity of the synthesized frameworks, TGA and
PXRD were carried out. The similarity of the PXRD data with
the simulated patterns based on single crystal data conrms the
phase purity of the as-synthesized samples (Figure S2,
Supporting Information). The PXRD patterns of the desolvated
compounds 16 show that they retain their crystallinity after
pretreatment at 100 C for 12 h. TGA analysis shows that after
the loss of lattice solvent molecules all the frameworks are quiet
stable up to a moderately high temperature (Figure S5,
Supporting Information). Further, details of the TGA are in the
Supporting Information.

through COOH groups, while the -NH2 group also

coordinates to another Cd(II) ion giving a (2-1-2)-(1)(1)-4 coordination mode. Both the NH2-H2BDC and BPz
ligands were also used by Lin et al.66 with Zn (II) ions where
they obtained a 3D porous MOF with six connected topology.
But coordination from the -NH2 group was not observed in
their case. The dihedral angle between the two pyrazole rings is
58.81, which is the lowest among complexes 16 with exobidentate coordination mode. The BDC2 molecule connects
to the Cd(II) ion in such a way that it forms a neutral double
layer type 2D structure along the b-axis, which is shown in
Figure S4, Supporting Information. These layers are further
connected by BPz molecules to form a 3D porous MOF
(Figure 3b) with irregular-shaped pores along the b-axis that are
lled with disordered solvent molecules. The methyl groups of
BPz blocked the channels in such a way that it formed cages
which are connected to each other through a small opening and
that is revealed from the analysis of Connolly surface as shown
in Figure 3d. The disordered solvent molecules were removed
by SQUEEZE command. Also, the total solvent accessible
volume is found to be 24.4% (822.0 3 out of 3364.1.4 3).
Better insight into the complicated 3D architecture can be
achieved by topological analysis. Th cluster method in
TOPOS67 has to be applied as there are carboxylate bridged
dinuclear Cd(II) ions. The dinuclear Cd(II) center has been
assigned an eight-connected node, the other mononuclear
Cd(II) center is considered as a four connected node, while the
two NH2-BDC2 ligands were considered as three connected
nodes. Finally, the analysis revealed the complex to be a 3,3,4,8c net with stoichiometry (3-c)2(3-c)2(4-c)2(8-c) having a 4nodal net (Figure 3c). It has a Point symbol of {42.64}2{42.6}4{44.610.88.106}, which is assigned to a new topological type,
having the name skr1 (topos & RCSR.ttd).
Structural Description of Complex 6. The asymmetric
unit of 6 contains one molecule each of Co(II) ion, BPz, and
BDC2 along with one coordinated water molecule. The Co(II)
ion is coordinated from three oxygen atoms of two BDC2, two
nitrogen atoms of pyrazole, and one oxygen atom of
coordinated water molecule in an CoO4N2 environment giving
it a distorted octahedral geometry (Figure 4a). The Co(II)O
F

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Figure 5. (a) Gas adsorption isotherms of compounds (a) 1, (b) 2, (c) 3, (d) 4, (e) 5 at 195 K (CO2, CH4) and 77 K (N2), (f) Selectivity of CO2
over N2 in 15 at 273 K, and (g) selectivity of CO2 over CH4 in 15 at 273 K.

Sorption Studies. The CO2 sorption studies of complexes

13 reveal that the isotherms are quiet similar owing to their
similar isostructural features and showed complete reversibility
and no or little hysteresis with a typical type I adsorption curve.
As shown in Figure 5ac, the adsorption curves showed
selective sorption of CO2 gas at 195 K as compared to CH4 (at
195 K) and N2 (at 77 K). The CO2 sorption increases abruptly
at low pressures and reaches a maximum uptake of 91, 81, and
87 mL g1 at 1 atm. In comparison, sorption of CH4 and N2 at
195 and 77 K is very less, which amounts to only a maximum
uptake of 10 mL g1 of CH4 and 11 mL g1 of N2 at
atmospheric pressure. This can be due to the comparably large
kinetic diameter of N2 (3.6 ) and CH4 (3.8 ) than CO2 (3.3
); furthermore the low kinetic energy of the N2 molecules at
77 K does not allow entering of the small windows of 13.
Moreover, at atmospheric pressure, the CO2 uptakes of 13 at
273 K reach 26.8, 27.5, and 27 mL g1, respectively (Figure S6,
Supporting Information). For complexes 4 and 5, the CO2
uptake at 195 K reaches a value of 42.3 and 37.2 mL g1 at 1
atm (Figure 5d,e). The open hysteresis loop of CO2 in 5 may
be attributed to the phenomenon of capillary condensation.68

The other possible reason could be the incomplete equilibrium

during the adsorption stage at low temperature and low
pressure region.69 This happens because at low temperature
diusion and mobility of molecules is slower. The Brunauer
EmmettTeller (BET) surface areas were estimated from the
CO2 isotherms at 298 K to be 405400 m2/g for 13 and 147
and 132 m2/g for 4 and 5, respectively. The surface areas of
complexes 13 are comparable to some of the reported porous
MOFs.70,71
We have also calculated the isosteric heat of adsorption (Qst)
for CO2 using adsorption data collected at 298 and 273 K
(Figure S7, Supporting Information). At the onset of
adsorption, Qst for compounds 13 is in the range of 74.2
67.6 kJ/mol, which is comparable to the Qst value in MIL-100
(63 kJ/mol),72 and reecting a strong and selective interaction
of CO2 with the framework. From the crystal structures of 13
it can be seen that all the carboxylate groups of BTC3 adopt a
monodentate binding mode; that is, one O atom remains free
in the polyhedral cages. In addition, one more interacting site
available for CO2 interaction inside the cage is the -NH moiety
of the BPz linker. The high Qst values of 13 are mainly due to
G

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Figure 6. Vapor adsorption isotherms of compounds (a) 1, (b) 2, and (c) 3.

g1).78 Complexes 2 and 3 also show similar types of sinusoidal

type adsorption curves (Figure 6b,c) with large hysteresis
resulting from dierent type of interactions at dierent pressure
points which indicates the presence of two energetically
dierent processes. Similar type of S shaped isotherm was
also observed in water sorption of MIL-101.79 The notable
hysteresis in the low pressure region indicates that the large
polyhedral cages retain some of the water molecules due to the
small window aperture. For 2 and 3, the water isotherms are
interrupted. This can be attributed to the accumulated water
molecules inside the cage which cannot escape easily during the
desorption process.80 Canivet et al. suggested that the
interruption can also arise from the weak exibility of the
framework (due to the rotation of the two pyrazole rings in BPz
ligand).81 As compared to high water sorption in 13,
methanol and ethanol uptake is very less and amounts to
nearly or equal to 100 mL g1 of methanol and 50 mL g1 of
ethanol at 1 atm. The small size of water molecules as
compared to methanol or ethanol could be the reason for high
uptake of water as there are no open metal or hydrophilic site
in 13. These studies reveal their possible application as a
desiccant material. Complexes 4 and 5 also show comparably
more water sorption than ethanol or methanol with nal uptake
of 90 and 110 mL g1 respectively (Figure S9a,b, Supporting
Information).
Solid State Emission Studies. The emission spectra of 4
and 5 were examined in the solid state at room temperature
(Figure 7). The free ligand BPz displays emission maxima at
422 nm. The complex 4 shows max at 430 nm, and 5 at 472
nm, under the excitation at 326 nm. As Zn(II) or Cd(II) is
dicult to oxidize or reduce due to the d10 conguration,
emission of 4 and 5 cannot be ascribed to LMCT or MLCT.
Thus, intraligand and ligand to ligand charge transitions are
responsible for emission properties of 4 and 5.82 The red shift
of 4 and 5 relative to BPz are 8 and 50 nm, respectively. These
red shifts may be attributed to ligand coordination to the metal

these polar sites inside the polyhedral cages. Furthermore, the

Qst for compound 5 (42 kJ/mol) is comparably higher than 4
(37.6 kJ/mol), which can be attributed to the presence of
additional -NH2 groups in 5, which provides additional
interacting sites for CO2 molecules.
The adsorption selectivities of CO2 with respect to N2 and
CH4 were calculated by the ideal adsorbed solution theory
(IAST) method.73 For this purpose, the sorption isotherms of
CO2, CH4, and N2 gases at 273 K were taken (Figures S6 and
S8, Supporting Information). The predicted adsorption
selectivities for equimolar CO2 and N2/CH4 mixtures in 15
are shown in Figure 5f,g. The selectivity of CO2 over N2 for 1
3 has values in the range of 6266 at 273 K. The selectivity
decreases with an increase in the bulk pressure. These values
are comparable to those of well-known porous MOFs.74 The
selectivity of CO2 could be attributed to the small aperture of
the windows which may discriminate between CO2 (small
kinetic diameter = 3.3 ) and N2 (kinetic diameter = 3.6 ) or
CH4 (kinetic diameter = 3.8 ). Additionally, the presence of
polar groups (-COOH and -NH) may be responsible for a
stronger CO2framework interaction due to a higher quadrupole moment of CO2. For complexes 4 and 5 selectivity values
are 29 and 34, respectively. A higher value for 5 than 4 can be
attributed to the extra -NH2 groups in the framework which
increases the interaction of CO2 molecules with the framework.
The selectivity values of CO2 over CH4 at 273 K for 15 are
15 for complexes 13, 5 for 4, and 7 for 5. Although these
values are less than CO2/N2 selectivity, they are still
comparable with some of the reported microporous
MOFs.7577
The solvent vapor sorption study of complexes 13 shows a
stepwise adsorption of water as a function of pressure. As
shown in Figure 6a, compound 1 exhibits a sinusoidal type
adsorption curve with a steep rise in adsorption after a pressure
threshold of 0.4 P/P0 with a saturation uptake of 350 mL g1,
which is greater than the well-known Zn-BTC MOF (208 mL
H

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Figure 7. Solid-state emission spectra of 4 and 5 at room temperature.

ion, which increases the rigidity of the ligand and reduces the
loss of energy by radiation less.

CONCLUSION
Using polycarboxylates and bipyrazole ligand and dierent
transition metal salts, we have successfully prepared six MOFs
out of which ve shows permanent porosity. Complexes 13
exhibit isostructural features having octahedral and cuboctahedral type cages with loh1 topology. Compound 4 exhibits a 1D
open channel, while compound 5 possesses a 3D network with
closed cages and exhibits a new topology having the name skr1.
Compound 6 has a nonporous 3D MOF with CdSO4 topology.
Complexes 15 exhibit selective CO2 sorption over N2 and
CH4. Complexes 13 also exhibit high water sorption with nal
amount of nearly 350 mL g1 at room temperature.
Compounds 4 and 5 exhibit solid state emission properties
with max at 430 and 472 nm.

ASSOCIATED CONTENT

S Supporting Information
*

More gas/vapor sorption isotherms, IR spectra, PXRD, TGA

plots, isosteric heat plots, table for bond distances and angles,
and extra images for compounds 16. This material is available
free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION

Corresponding Author

*E-mail: skonar@iiserb.ac.in.
Notes

The authors declare no competing nancial interest.

(R.R.) Undergraduate researcher.

ACKNOWLEDGMENTS
R.R. thanks IISER Bhopal for the INSPIRE fellowship. K.T.
thanks CSIR, New Delhi, India, for Research Associateship.
S.K. thanks CSIR and IISER Bhopal for generous nancial and
infrastructural support.

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