Polyhedron 171 (2019) 46–52

Contents lists available at ScienceDirect

Polyhedron
journal homepage: www.elsevier.com/locate/poly

Syntheses, structures and adsorption properties of two-dimensional

Cd(II) coordination polymers
Pradhumna Mahat Chhetri a,⇑, Xiang-Kai Yang b, Jhy-Der Chen b,⇑
a
Department of Chemistry, Amrit Campus, Tribhuvan University, Kathmandu, Nepal
b
Department of Chemistry, Chung Yuan Christian University, Chung-Li, Taiwan, ROC

a r t i c l e i n f o a b s t r a c t

Article history: Solvothermal reactions of Cd(CH3COO)2 and 2,20 -(1,3-phenylene)-bis(N-pyridin-3-yl)acetamide (1,3-

Received 2 June 2019 pbpa) with 1,3-phenylenediacetic acid (1,3-H2PDA), 4,40 -oxybis(benzoic acid) (4,40 -H2OBA) and 1,4-ben-
Accepted 30 June 2019 zenedicarboxylic acid (1,4-H2BDC) afforded [Cd(1,3-pbpa)(1,3-PDA)]n, 1, [Cd(1,3-pbpa)(OBA)2H2O]n, 2,
Available online 12 July 2019
and [Cd(1,3-pbpa)(1,4-BDC)(H2O)EtOHH2O]n, 3, respectively, which were structurally characterized as
two-dimensional (2D) coordination polymers. Complexes 1 and 2 show the rare {84122}{8}2-2,4L2 topol-
Keywords: ogy, whereas complex 3 adopts a new topology with a point symbol of {12}{4125}{4}, which can be fur-
Coordination polymers
ther simplified as the 44-sql topology and the 63-hcb topology, respectively. Desolvated product of 2
X-ray structure
Topology
shows a moderate uptake of CO2 and a good selectivity over N2, which also exhibits a better H2 and
Luminescence CO2 sorption compared to the activated product of 1, indicating the effect of ligand type on the adsorption
Gas sorption properties of 2D complexes with the 44-sql topology. Thermal gravimetric analysis (TGA) and the solid
state luminescence properties of 1–3 have also been investigated.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction On the basis of the above consideration and to investigate the

effect of ligand flexibility on the structural diversity, three new
Coordination polymers (CPs) have formed a highly decorated 2D CPs, [Cd(1,3-pbpa)(1,3-PDA)]n, 1, [Cd(1,3-pbpa)(OBA)2H2O]n,
and fascinating research area during the recent years not only 2, and [Cd(1,3-pbpa)(1,4-BDC)(H2O)EtOHH2O]n, 3, have been syn-
because of the intriguing structural diversity [1] but also due to thesized by the solvothermal reactions of Cd(CH3COO)2 and 2,20 -
the potential applications as zeolite-like materials for gas separa- (1,3-phenylene)-bis(N-pyridin-3-yl)acetamide (1,3-pbpa) with
tion, storage and sensing, catalysis, luminescence, magnetism, 1,3-phenylenediacetic acid (1,3-H2PDA), 4,40 -oxybis(benzoic acid)
electronics and dyes removing from industrial waste water and (4,40 -H2OBA) and 1,4-benzenedicarboxylic acid (1,4-H2BDC),
so on [2]. respectively. Herein, the synthesis, structures and adsorption prop-
Structural diversity is one of the attractive features in crystal erties of these complexes as well as their thermal and luminescent
engineering of CPs and it is influenced by various factors such as properties are reported.
identity of ligand and metal center, donor position in ligand, metal
to ligand ratio and flexibility of ligand [3]. Analysis of topologies of
2D CPs shows that sql and hcb network topologies are the most 2. Experimental
common [4], which offer ample opportunities to enhance and
modify the ability of potential application. Not only three-dimen- 2.1. General procedures
sional (3D) but also 2D CPs can be potential materials for different
gas adsorptions [5]. Hydrogen is a clean and pollution-free fuel for Elemental analyses were performed on a PE 2400 series II
transportation [6], while carbon monoxide is a primary greenhouse CHNS/O or an elementar Vario EL-III analyzer. IR spectra (KBr disk)
gas to cause the global warming. Therefore, investigation on the were obtained from a JASCO FT/IR-460 plus spectrometer. Thermal
adsorptions of H2 and CO2 has become an important subject in gravimetric analyses (TGA) measurements were carried out on a
the application of CPs [5b,7]. TG/DTA 6200 analyzer. Powder X-ray diffraction was performed
by using a Bruker D2 PHASER diffractometer with Cu Ka
⇑ Corresponding authors. Fax: +886 3 2653399. (ka = 1.54 Å) radiation. Gas adsorption experiments were carried
E-mail addresses: [email protected] (P. Mahat Chhetri), [email protected] out on a Micromeritics ASAP 2020 analyzer. Emission spectra were
(J.-D. Chen). recorded on a Hitachi F-4500 spectrometer.

https://doi.org/10.1016/j.poly.2019.06.056
0277-5387/Ó 2019 Elsevier Ltd. All rights reserved.
 P. Mahat Chhetri et al. / Polyhedron 171 (2019) 46–52 47

2.2. Materials Table 1

Crystal data for complexes 1–3.

The reagent 1,3-phenylenediacetic acid was purchased from Compound 1 2 3

ACROS Co., and 4,40 -oxybis(benzoic acid) (4,40 -H2OBA), 1,4-ben- Formula C30H26CdN4O6 C34H30CdN4O9 C30H32CdN4O9
zenedicarboxylic acid (1,4-H2BDC) and cadmium(II) acetate salt Fw 650.95 751.02 704.99
from Alfa Aesar Co. The 1,3-pbpa ligand was synthesized according Crystal System monoclinic monoclinic triclinic
to published procedures [8]. Space Group P21 P21/c Pı
Unit cell dimensions
a (Å) 10.0498(2) 13.1239(2) 6.4854(2)
2.3. Preparations b (Å) 13.8571(2) 27.9104(5) 15.2191(5)
c (Å) 10.7401(2) 9.5687(2) 15.9376(5)
2.3.1. [Cd(1,3-pbpa)(1,3-PDA)]n (1) a (°) 90 90 96.151(2)
b (°) 112.3780(10) 110.8650(10) 92.100(2)
A mixture of Cd(CH3COO)2 (0.023 g, 0.10 mmol), 1,3-pbpa c (°) 90 90 96.96(2)
(0.035 g, 0.10 mmol) and 1,3-phenylenedicacetic acid (0.019 g, V (Å3) 1383.04(4) 3275.10(11) 1550.50(9)
0.10 mmol) in 7 mL of ethanol was sealed in a 23 mL Teflon-lined DCalc. (g cm3) 1.563 1.523 1.510
stainless steel autoclave, which was heated under autogenous F(0 0 0) 660 1528 720
Z 2 4 2
pressure at 120 °C for 48 h followed by slow cooling at a rate of m(Mo Ka) (mm1) 0.841 0.728 0.763
2 °C h1 to RT. Needle-shaped colorless crystals were obtained on Range (2h) for data 4.098–56.662 2.918–56.614 3.524–56.938
slow cooling which were collected and characterized by using sin- collection (°)
gle-crystal X-ray diffraction. Yield: 0.056 g (86%). Anal. Calc. for Reflections collected 25 569 32 450 28 859
Independent reflections 6898 8145 7781
C30H26CdN4O6 (MW = 650.95): C, 55.35; N, 8.61; H, 4.03. Found:
[Rint = 0.0197] [Rint = 0.0226] [Rint = 0.0319]
C, 54.98; N, 8.53; H, 4.00 %. IR (cm1): 418(w), 443(w), 499(w), Data/ 6898/1/371 8145/0/433 7781/0/406
519(w), 546(m), 583(m), 637(m), 666(m), 703(s), 753(s), 804(m), restraints/parameters
826(m), 932(w), 1052(m), 1129(m), 1153(m), 1193(m), 1246(m), Quality-of-fit indicatorc 1.034 1.019 1.013
1276(m), 1325(s), 1424(s), 1475(s), 1549(s), 1691(s), 3061(m), Final R indices [I > 2r(I)]a,b R1 = 0.0214 R1 = 0.0432 R1 = 0.0271
wR2 = 0.0450 wR2 = 0.1126 wR2 = 0.0630
3112(m), 3289(s), 3440(s).
R indices (all data) R1 = 0.0241 R1 = 0.0573 R1 = 0.0333
wR2 = 0.0460 wR2 = 0.1223 wR2 = 0.0659
2.3.2. [Cd(1,3-pbpa)(4,40 -OBA)2H2O]n (2)
R1 = R||Fo|  |Fc||/R|Fo|. bwR2 = [Rw(F2o  F2c )2/Rw(F2o)2]1/2. w = 1/[r2(F2o)+(ap)2+(bp)],
Compound 2 was prepared by following the procedure p = [max(F2o or 0) + 2(F2c )]/3. a = 0.0243, b = 0, 1; a = 0.0596, b = 2.9753, 2; a = 0.0307,
described for 1 except a mixture of Cd(CH3COO)2 (0.023 g, b = 0.5951, 3. cQuality-of-fit = [Rw(|F2o|  |F2c |)2/Nobserved  Nparameters)]1/2.
0.10 mmol), 1,3-pbpa (0.035 g. 0.10 mmol) and 4,40 -oxybis(benzoic
acid) (0.026 g, 0.10 mmol) in 7 mL of water was used. Needle-
shaped colorless crystals were obtained. Yield: 0.055 g (73 %). Anal. ing to crystal parameters and structure refinement is summarized
Calc. for C34H30CdN4O9 (MW = 751.02): C, 54.37; N, 7.46; H, 4.03. in Table 1.
Found: C, 54.20; N, 7.58; H, 4.24 %. IR (cm1): 524(w), 638(m),
661(m), 700(m), 738(m), 785(m), 806(m), 879(m), 916(w), 960 3. Results and discussion
(w), 1016(w), 1054(w), 1099(w), 1130(m), 1160(m), 1196(m),
1242(s), 1280(m), 1400(s), 1425(s), 1481(m), 1545(s), 1597(s), 3.1. Crystal structure of 1
1670(m), 3064(m), 3260(m), 3536(w).
The single crystal X-ray diffraction analysis revealed that the
2.3.3. [Cd(1,3-pbpa)(1,4-BDC)(H2O)EtOHH2O]n (3) crystals of 1 conform to the monoclinic crystal system with the
Compound 3 was prepared by following the procedure space group P21 and each asymmetric unit contains one Cd(II)
described for 1 except a mixture of Cd(CH3COO)2 (0.023 g, ion, one 1,3-pbpa and one 1,3-PDA2. Fig. 1(a) depicts a coordina-
0.10 mmol), 1,3-pbpa (0.035 g. 0.10 mmol) and 1,4-benzenedicar- tion environment about the metal ion. The Cd(II) ion is coordinated
boxylic acid (0.017 g, 0.10 mmol) in 8 mL of ethanol and 2 mL of with two pyridyl nitrogen atoms [CdAN = 2.293(2) and 2.312(2) Å]
water was used. Needle shape colorless crystals were obtained. from two 1,3-pbpa and four oxygen atoms [CdAO = 2.223(3), 2.279
Yield: 0.032 g (45 %). Anal. Calc. for C30H32CdN4O9 (2), 2.408(19) and 2.57(2) Å] from two 1,3-PDA2 ligands, resulting
(MW = 704.99): C, 51.11; N, 7.95; H, 4.56. Found: C, 50.45; N, in a distorted octahedral geometry. The 1,3-PDA2 ligands bridge
7.85; H, 4.29%. IR (cm1): 523(w), 638(w), 702(w), 748(m), 838 the metal ions with the l2-j1,j1,j1,j1 bonding mode, forming
(w), 953(w), 1016(w), 1053(w), 1130(w), 1196(w), 1244(w), one dimensional helical chains having 13.9 Å span of period,
1296(m), 1338(w), 1384(m), 1485(m), 1558(s), 1614(m), 1686 Fig. 1(b), which are also connected by the 1,3-pbpa ligands to form
(m), 3068(w), 3111(w), 3263(m), 3442(w), 3633(w). a 2D structure, Fig. 1(c). Topologically, if the ligands are considered
as 2-connection nodes (due to the flexibility), the structure of 1 can
2.4. X-ray crystallography be simplified as a 2D net with the rare {84122}{8}2-2,4L2 topology,
as shown in Fig. 1(d), which can also be further simplified into the
A suitable single crystal of 1–3 was fixed by epoxy adhesive on 44-sql topology if the ligands are considered as linkers. The cova-
the tip of glass fiber and kept in goniometer head on Bruker AXS lently bonded 2D layers stack along the a-axis in crystal packing
SMART APEX II CCD diffractometer at 22 °C, which was equipped and interact with each other through NAH  O hydrogen bonding
with a graphite-monochromated Mo Ka (ka = 0.71073 Å) radiation [H  O = 2.102 and 2.240 Å; \NAH  O, 158.8 and 173.2°] from
for data collection [9]. Data was integrated using the Bruker APEX3 the amide hydrogen atoms to the carboxylate oxygen atoms to
software program and the structure factors were obtained after extend into a 3D structure, Fig. S1 and Table S1.
Lorentz and polarization, followed by empirical absorption correc-
tion based on ‘‘multi-scan”. The structures were solved with the 3.2. Crystal structure of 2
SHELXTLsoftware using direct methods and refined by full-matrix
least squares minimization [10]. All hydrogen atoms were added The single crystal X-ray diffraction analysis revealed that crys-
by using the HADD command in SHELXTL. Basic information pertain- tals of 2 adopt the monoclinic crystal system with the space group
48 P. Mahat Chhetri et al. / Polyhedron 171 (2019) 46–52

2.298(2) Å] from two 1,3-pbpa and four oxygen atoms

[CdAO = 2.257(2), 2.438(2), 2.307(2) and 2.433(2) Å] from two
4,40 -OBA2, resulting in a distorted octahedral geometry. The coor-
dination environment of Cd(II) ion is depicted in Fig. 2(a). Individ-
ually, N-donor linker and O-donor linker form 1-D helical chain
which are in alternate arrangement as shown in Fig. 2(b)–(d).
Topologically, the structure of complex 2 can be simplified as a
2D layer with the rare {84122}{8}2-2,4L2 topology, as shown in
Fig. 1(d), which can also be further simplified into the 44-sql topol-
ogy if the ligands are considered as linkers. In the crystal packing,
the 2D layers stack along a-axis and interact with hydrogen bond-
ing. The co-crystallized water molecules interact with each other
and with amide oxygen and carboxylate oxygen atoms through
the OAH  O hydrogen bonding [H  O = 1.77–2.34 Å;
\OAH  O = 145.3–170.0°] to extend into a 3D supramolecular
structure, as shown in Fig. S2 and Table S2.

3.3. Crystal structure of 3

The single crystal X-ray diffraction analysis revealed that the

crystals of 3 adopt the triclinic crystal system and space group Pı.

Fig. 1. (a) A representative drawing showing coordination environment for 1.

Symmetry transformations used to generate equivalent atoms: (A) 1  x, 1/2 + y,
1  z; (B) 1 + x, y, 1 + z. (b) A drawing showing the 1D helical chain afforded by
1,3-PDA2 on 1. (c) A drawing showing the 2D structure. (d) A drawing showing the
2,4L2 topology. (e) A drawing showing the sql topology.

Fig. 2. (a) A representative drawing showing coordination environment for 2.

P21/c. The asymmetric unit contains one Cd(II) ion, one 1,3-pbpa, Symmetry transformations used to generate equivalent atoms: (A) 2  x, 1/2 + y,
3/2  z; (B) 1  x, 1/2 + y, ½  z (b) A drawing showing the 1D helical chain
one 4,40 -OBA2 and two water molecules. The Cd(II) ions is coordi-
afforded by 4,40 -OBA2 for 2. (c) A drawing showing the 1D helical chain afforded by
nated with two pyridyl nitrogen atoms [CdAN = 2.324(2) and 1,3-pbpa for 2. (d) 2D structure in c axis for 2 showing both helical chains.
 P. Mahat Chhetri et al. / Polyhedron 171 (2019) 46–52 49

The asymmetric unit contains one Cd(II) ion, one 1,3-pbpa, one 1,4- [OAH  O = 1.884–2.299 Å; \OAH  O = 141.6–172.2°] hydrogen
BDC2, two water molecules and one ethanol molecule. Each of the bonds from the co-crystallized water molecules, coordinated water
Cd(II) ions is coordinated with two pyridyl nitrogen atoms molecules and ethanol molecules to the carboxylate oxygen atoms,
[CdAN = 2.3024(16) and 2.3337(16) Å] in trans-position from two co-crystallized water molecules and amide oxygen atoms.
1,3-pbpa, four oxygen atoms [CdAO = 2.3659(13), 2.3757(14), NAH  O hydrogen bonds originating from the amine hydrogen
2.4011(14) and 2.5046(14) Å] from two 1,4-BDC2 and one oxygen atoms to the carboxylate oxygen atoms (H  O = 2.098 Å;
from coordinated water [CdAO = 2.424(15) Å], resulting in a dis- \NAH  O = 171.7°) and to the ethanol oxygen atoms
torted pentagonal bipyramidal geometry. The coordination envi- (H  O = 2.093 Å; \NAH  O = 153.8°) are also observed. The pi-pi
ronment of Cd(II) ion is depicted in Fig. 3(a). The metal ions are stacking interactions (3.88 Å) between centroid of pyridyl ring
bridged by the 1,4-BDC2 ligands to form 1D zig-zag chains which assist to extend 3D supramolecular structure as shown in Fig. S3
are also interlinked by 1,3-pbpa ligands to construct a 2D structure and Table S3.
as shown in Fig. 3(b). Topologically, the structure of 3 can be sim-
plified as a 2D net with the {12}{4125}{4} topology, Fig. 3(c), 3.4. Ligand conformation and structural diversity
which can also be further simplified to the hcb topology if the
ligands are considered as linkers. In the crystal packing, the 2D lay- The conformation of 1,3-pbpa is determined by the orientations
ers stacking along a-axis are supported by the OAH  O of C@O or NAH pairs and the orientations of the pyridyl nitrogen
and amide oxygen. If the orientation of C@O or NAH pair are on
the same direction, it is defined as ‘‘cis” and on the opposite direc-
tion, ‘trans’. By considering the orientations of pyridyl nitrogen and
amide oxygen, syn–syn, anti–anti and syn–anti are specified [11].
Accordingly, the conformations of 1,3-pbpa are cis syn–syn in 1,
trans syn–syn in 2 and cis anti–anti in 3, indicating the flexibility
of the 1,3-pbpa ligand that is subject to the change of the auxiliary
dicarboxylate ligand.
Structural diversity in 1–3 is highly influenced by flexibility of
the dicarboxylate ligands. While the flexible 1,3-PDA2 and 4,40 -
OBA2 bridge the 1,3-pbpa–Cd(II)-based 1D chains to form helical
2D structures with the sql topology for 1 and 2, the rigid 1,4-BDC2
ligands in 3 direct the formation of a 2D layer with the hcb
topology.

3.5. Thermal properties

To investigate the thermal properties, we first checked the puri-

ties of complexes 1–3 by measuring their powder X-ray diffraction
patterns. Figs. S4–S6 show that the powder patterns of these two
complexes match quite well with those simulated from single-
crystal X-ray data, indicating the bulk purities of these complexes.
Thermal gravimetric analysis (TGA) of complexes 1–3 have been
carried out in nitrogen atmosphere from 30 to 900 °C, Fig. 4 and
Table 2. Complex 1 is stable up to 300 °C which shows first weight
loss in 300–650 °C corresponding to loss of N-donor ligand (obs.
51.85%, Calc. 53.21%). The second weight loss in 650–850 °C can
be ascribed to loss of dicarboxylate ligand (obs. 27.55%, Calc.
29.52%). Complex 2 exhibits first weight loss of 4.8 % (Calc. 5.1%)

Fig. 3. (a) A representative drawing showing coordination environment for 3.

Symmetry transformations used to generate equivalent atoms: (A) x, y, z. (b)
2D structure for 3 showing 1D chain formed by 1,4-BDC2 and circular ring by 1,3-
pbpa. (c) Topology for 3 having point symbol {12}{4125}{4}. (d) A drawing showing
the hcb topology. Fig. 4. TGA curve of 1–3.
50 P. Mahat Chhetri et al. / Polyhedron 171 (2019) 46–52

Table 2 Activated sample of complex 1 (10 ) shows comparable hydrogen

TGA data for 1–3. (9.72 cm3g1) and nitrogen (9.42 cm3g1) sorption at 77 K even
Compound Wt. loss of guest Wt. loss of ligands, °C though the kinetic diameter of nitrogen (3.64 Å) is greater than
molecules, °C [obs/Calc, %] [obs./Calc, %] hydrogen (2.89 Å), whereas the CO2 (kinetic diameter, 3.30 Å)
1 300–900 [83.67/82.73] adsorption is 6.16 cm3 g1 at 273 K and 4.87 cm3 g1 at 298 K,
2 50–300 [4.8/5.1] 300–900 [81.71/80.24] respectively, Fig. S7. Activated sample of complex 2 (20 ) shows
3 55–300 [9.75/9.08] 300–600 [74.9/71] more H2 uptake of 15.28 cm3 g1 compared to the N2 uptake of
7.16 cm3 g1 at 77 K whereas the CO2 adsorption is 12.48 cm3g1
in 50–300 °C corresponding to loss of two cocrystallized water at 273 K and 6.46 cm3g1 at 298 K, respectively, Fig. S8. Figs. 6
molecules. The second weight loss of 81.71 % (Calc. 80.24%) in and 7 show that 20 exhibits better H2 (77 K) and CO2 (273 K)
300–900 °C is due to the loss of ligands. Complex 3 shows first adsorption than N2 (77 K), while Figs. 8 and 9 show that 20 uptakes
weight loss of 9.75 % (Calc. 9.08%) in 55–300 °C corresponding to more H2 and CO2 than 10 respectively Table 3. The low gas adsorp-
loss of cocrystallized one water, one ethanol and coordinated one tion of these activated samples are presumably due to the interdig-
water molecules, while the second weight loss of 74.9% (Calc. itated framework and nonporous in nature. The large hysteresis in
71%) in 300–600 °C is attributed to the weight loss of ligands. the adsorption isotherms can be ascribed to the adsorbate–adsor-
bent interaction because of the presence of polar amide function
group in 1,3-pbpa [13]. The stabilities of 10 and 20 after the adsorp-
3.6. Thermal stability and structural transformation
tions process were confirmed by using the PXRD patterns, Figs. S9
and S10, which were similar to those of the as-synthesized
The thermal stabilities of 2 and 3 upon solvent removal were
complexes.
investigated by heating 2 and 3 at 180 and 150 °C, respectively.
Because of absence of solvent in 1, solvent accessible void can-
Fig. S5(c) shows that the PXRD pattern of 2 heated at 180 °C
not be calculated by using the PLATON. Therefore, CrystalExplorer 17
remains the same as the simulated pattern, indicating the thermal
stability upon solvent removal. When 3 was heated at 150 °C, the
PXRD patterns changed as shown in Fig. 5(c), indicating structural
transformation upon solvent removal. To check the reversibility of
the structural transformation, the desolvated product was then
immersed separately into two solvent systems which are a mixture
of ethanol and water (4:1 ratio, i.e. initial complex preparation sol-
vent ratio) and only ethanol. Fig. 5(e) demonstrates that the sol-
vent system containing both ethanol and water cannot revert the
structural change and only ethanol was able to transform the des-
olvated product into the original one, although some few modified
peaks indicating the presence of defects in Fig. 5(d) can be
observed, which are probably due to the distortion in coordination
environment of metal center.

3.7. Gas adsorption

Complexes 1 and 2 provide a unique opportunity to investigate

the effect of dicarboxylate ligand on the adsorption properties of
2D CPs with the sql topology. The gas adsorption (CO2 at 273
and 298 K; N2 and H2 at 77 K) of the activated samples has been
carried out even though the solvent accessible void in 2 in dehy- Fig. 6. N2 (blue) and H2 (red) sorption isotherm for 20 .
drated framework is 224.6 Å3 (6.9%) calculated by using PLATON
[12], where the unit cell volume is 3275.1 Å3.

Fig. 5. Powder X-ray patterns of 3 (a) simulation, (b) experimental and (c) at 150 °C
(d) kept into EtOH after heated at 150 °C (e) kept into mixture of EtOH and H2O after
heated at 150 °C. Fig. 7. N2 (blue) and CO2 (red) sorption isotherm for 20 . (Color online.)
 P. Mahat Chhetri et al. / Polyhedron 171 (2019) 46–52 51

Table 4
Excitation and emission of complexes 1–3, dicarboxylic acids and 1,3-pbpa.

Compound Excitation (kmax) Emission (kmax)

1 303 322
2 277/327 378
3 278/315 375
1,3-pbpa 335 381
4,40 -OBA 279 316
1,4-BDC 278/327 380

Fig. 8. H2 sorption isotherms for 10 (red) and 20 (blue). (Color online.)

Fig. 10. Normalized emission and excitation spectra of 1–3.

observed. The 1,3-pbpa, 4,40 -H2OBA and 1,4-H2BDC show emis-

sions at 381, 316 and 380 nm upon excitation at 335, 279 and
278/327 nm, respectively, Figs. S11 and S12, which can be ascribed
to the intraligand p* to n or p* to p transitions. Fig. 10 shows the
maximum emission wavelengths of 1, 2 and 3 at 322, 378 and
375 nm upon excitation at 303, 277/327 and 278/315 nm, respec-
tively. Due to the d10 electronic configuration, the Cd(II) ion hardly
undergoes oxidation and reduction. The emissions in 1–3 are thus
not due to ligand-to-metal charge transfer (LMCT) or metal-to-
ligand charge transfer (MLCT) and maybe attributable to intrali-
Fig. 9. CO2 sorption isotherms for 10 (red) and 20 (blue). (Color online.)
gand charge transfer (ILCT) or ligand-to-ligand charge transfer
(LLCT) from 1,3-pbpa and dicarboxylate ligands [15].

Table 3
Gas sorption data for activated sample of 1 and 2. 4. Conclusions
Gas Activated sample of 1 Activated sample of 2
Uptake cm3 g1 (Temp.) Uptake cm3 g1 (Temp.) Three 2D Cd(II) CPs with 1,3-pbpa and different dicarboxylate
coligands have been synthesized and structurally characterized.
H2 9.72 (77 K) 15.28 (77 K)
N2 9.42 (77 K) 7.16 (77 K)
The structural diversity is highly influenced by the flexibility of
CO2 6.16 (273 K) 12.48 (273 K) the dicarboxylate ligands. While the flexible 1,3-PDA2 and
4.87 (298 K) 6.46 (298 K) 4,40 -OBA2 ligands direct the 2D helical structures with the sql
topology for 1 and 2, the rigid 1,4-BDC2 ligands in 3 lead to the
formation of a 2D layer with the hcb topology, resulting in cis
[14] is adopted to calculate crystal void of 1 using default isovalue syn–syn, trans syn–syn and cis anti–anti conformations for 1,3-pbpa
of 0.002 e au3. The calculated crystal void volume of 1 i.e. in 1, 2 and 3, respectively. Gas adsorption experiments show that
192.08 Å3 is less than the solvent accessible volume of 2, which the desolvated product of 2 exhibits a moderate CO2 uptake and
is 224.6 Å3, probably indicating that 20 may show better gas sorp- a good selectivity over N2 adsorption and better H2 and CO2
tion than 10 . adsorptions compared to the activated product of 1. This study
provides an insight into understanding the effect of the auxiliary
dicarboxylate ligands on the adsorption properties of the 2D CPs
3.8. Photoluminescence
with the sql topology.

The luminescent properties of complexes 1–3 and free ligands

1,3-pbpa, 1,3-H2PDA, 4,40 -H2OBA and 1,4-H2BDC were investigated Acknowledgement
at room temperature in solid state. The maximum excitation and
emission wavelengths of 1,3-pbpa, 4,40 -H2OBA, 1,4-H2BDC and 1– We are grateful to the Ministry of Science and Technology of the
3 are listed in Table 4, while the emission of 1,3-H2PDA was not Republic of China for support.
52 P. Mahat Chhetri et al. / Polyhedron 171 (2019) 46–52

Appendix A. Supplementary data (i) X. Liu, Z. Xiao, A. Huang, W. Wang, L. Zhang, R. Wang, D. Suna, New J. Chem.
40 (2016) 5957.
[4] (a) L. Carlucci, G. Ciani, D.M. Proserpio, T.G. Mitina, V.A. Blatov, Chem. Rev. 114
CCDC 1905006–1905008 contains the supplementary (2014) 7557;
crystallographic data for 1–4. These data can be obtained free of (b) Y.-B. Zhang, H. Furukawa, N. Ko, W.-X. Nie, H.J. Park, S. Okajima, K.E.
Cordova, H.-X. Deng, J. Kim, O.M. Yaghi, J. Am. Chem. Soc. 137 (2015) 2641;
charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
(c) Y.-J. Cui, T. Song, J.-C. Yu, Y. Yang, Z.-Y. Wang, G.-D. Qian, Adv. Funct. Mater.
from the Cambridge Crystallographic Data Centre, 12 Union Road, 25 (2015) 4796;
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: (d) L.E. Kreno, K. Leong, O.K. Farha, M. Allendorf, R.P. Van Duyne, J.T. Hupp,
Chem. Rev. 112 (2012) 1105.
[email protected]. Supplementary data to this article can
[5] (a) S. Chand, S.M. Elahi, A. Pal, M.C. Das, Dalton Trans. 46 (2017) 9901;
be found online at https://doi.org/10.1016/j.poly.2019.06.056. (b) J.-R. Li, R.J. Kuppler, H.-C. Zhou, Chem. Soc. Rev. 38 (2009) 1477;
(c) S.C. King, R.-B. Lin, H. Wang, H.D. Arman, B. Chen, Mater. Chem. Front. 1
References (2017) 1514;
(d) A. Kondo, H. Noguchi, L. Carlucci, D.M. Proserpio, G. Ciani, H. Kajiro, T.
Ohba, H. Kanoh, K. Kaneko, J. Am. Chem. Soc. 129 (2007) 12362;
[1] (a) E.R.T. Tiekink, J.J. Vittal, Frontiers in Crystal Engineering, John Wiley & Sons (e) W. Yang, B. Li, H. Wang, O. Alduhaish, Cryst. Growth Des. 15 (2015) 2000;
Ltd, England, 2006; (f) L. Han, Y. Yan, F. Sun, K. Cai, T. Borjigin, X. Zhao, F. Qu, G. Zhu, Cryst. Growth
(b) N.W. Ockwig, O. Delgado-Friedrichs, M. O’Keeffe, O.M. Yaghi, Acc. Chem. Des. 13 (2013) 1458.
Res. 38 (2005) 176; [6] (a) K.M. Thomas, Dalton Trans. (2009) 1487;
(c) J.J. Vittal, Coord. Chem. Rev. 251 (2007) 1781; (b) M.P. Suh, H.J. Park, T.K. Prasad, D.-W. Lim, Chem. Rev. 112 (2012) 782.
(d) G.K. Kole, J.J. Vittal, Chem. Soc. Rev. 42 (2013) 1755. [7] K. Sumida, D.L. Rogow, J.A. Mason, T.M. McDonald, E.D. Bloch, Z.R. Herm, T.-H.
[2] (a) J.-R. Li, J. Sculley, H.-C. Zhou, Chem. Rev. 112 (2012) 869; Bae, J.R. Long, Chem. Rev. 112 (2012) 724.
(b) M. O’Keeffe, M.A. Peskov, S.J. Ramsden, O.M. Yaghi, Acc. Chem. Res. 41 [8] (a) P. Mahat Chhetri, X.-K. Yang, J.-D. Chen, Cryst. Growth Des. 17 (2017) 4801;
(2008) 1782; (b) P. Mahat Chhetri, X.-K. Yang, J.-D. Chen, CrystEngComm 20 (2018) 2126.
(c) M. Yoon, R. Srirambalaji, K. Kim, Chem. Rev. 112 (2012) 1196; [9] Apex2, V2008.6; Sadabs V2008/1; Saint+ V7.60A; Shelxtl V6.14; Bruker AXS
(d) Z.-C. Hu, B.J. Deibert, J. Li, Chem. Soc. Rev. 43 (2014) 5815. Inc.: Madison, Wisconsin, USA, 2008.
[3] (a) X.-Y. Wan, F.-L. Jiang, L. Chen, M.-Y. Wu, M.-J. Zhang, J. Pan, K.-Z. Su, Y. [10] G.M. Sheldrick, Acta Crystallogr. Sect. A 64 (2008) 112.
Yang, M.-C. Hong, Cryst. Growth Des. 15 (2015) 1481; [11] (a) H.-Y. He, C.-H. Hsu, H.-Y. Chang, X.-K. Yang, P. Mahat Chhetri, D.M.
(b) M.-N. Chang, X.-K. Yang, P. Mahat Chhetri, J.-D. Chen, Polymers 9 (2017) Proserpio, J.-D. Chen, Cryst. Growth Des. 17 (2017) 1991;
691; (b) H.-Y. He, X.-K. Yang, P. Mahat Chhetri, C.-H. Hsu, M.-N. Chang, J.-D. Chen,
(c) M. Oh, C.L. Stern, C.A. Mirkin, Inorg. Chem. 44 (2005) 2647; Polyhedron 133 (2017) 92.
(d) J.-J. Cheng, Y.-T. Chang, C.-J. Wu, Y.-F. Hsu, C.-H. Lin, D.M. Proserpio, J.-D. [12] A.L. Spek, J. Appl. Cryst. 36 (2003) 7.
Chen, CrystEngComm 14 (2012) 537; [13] D.K. Maity, A. Halder, S. Ghosh, D. Ghoshal, Cryst. Growth Des. 16 (2016) 4793.
(e) F.-Y. Ge, X. Ma, D.-D. Guo, L.-N. Zhu, Z.-P. Deng, L.-H. Huo, S. Gao, Cryst. [14] M.J. Turner, J.J. McKinnon, S.K. Wolff, D.J. Grimwood, P.R. Spackman, D.
Growth Des. 17 (2017) 2667; Jayatilaka, M.A. Spackman, CrystalExplorer17, University of Western Australia,
(f) K. Nath, A. Husain, P. Dastidar, Cryst. Growth Des. 15 (2015) 4635; 2017, http://hirshfeldsurface.net.
(g) D.-S. Liua, Y. Suia, G.-M. Yea, H.-Y. Wanga, J.-Q. Liua, W.-T. Chen, J. Solid [15] (a) L.-F. Ma, L.-Y. Wang, J.-L. Hu, Y.-Y. Wang, G.-P. Yang, Cryst. Growth Des. 9
State Chem. 263 (2018) 182; (2009) 5334;
(h) T.-T. Wu, W. Hsu, X.-K. Yang, H.-Y. He, J.-D. Chen, CrystEngComm 17 (2015) (b) Y. Gong, J. Li, J. Qin, T. Wu, R. Cao, J. Li, Cryst. Growth Des. 11 (2011) 1662.
916;