Zinc(ii) coordination polymers with substituted benzenedicarboxylate and tripodal imidazole ligands: Syntheses, structures and properties

Article abstract of DOI:10.1039/c4ce00835a

By introducing 1,4-benzenedicarboxylic acid (H₂BDC) with different substituent groups H₂BDC-R (R = NH₂, OH, NO ₂) into the Zn(ii)-1,3,5-tris(1-imidazolyl)benzene (tib) system, four new zinc(ii) coordination polymers, namely [Zn₅(tib) ₂(BDC-NH₂)₄(μ₂-OH) ₂]·H₂O (1), [Zn₂(tib)(BDC-NH ₂)SO₄(H₂O)₂]·5H₂O (2), [Zn₂(tib)₂(HBDC-OH)₂(BDC-OH)] ·2H₂O (3) and [Zn(tib)(BDC-NO₂)]·H ₂O (4), have been successfully synthesized under solvothermal conditions. Complexes 1 and 2 based on the same H₂BDC-NH₂ show different structures: 1 is a 3-fold interpenetrated 3D framework with point (Schlaefli) symbol {5³·6²·7} ₂{5³}₂{5⁸·6 ²·8⁵}, while 2 exhibits a 2D network with {6 ²·8⁴}{6²·8}₄ topology. 3 and 4 are 2D networks with different topologies of {6³} and {4⁴·6²}, respectively. The structural diversity of 1-4 indicates that the substituent groups of H₂BDC as well as the reaction temperature and solvent play an important role in determining the framework structures and topologies. Furthermore, the sorption and photoluminescence properties of the complexes were investigated. This journal is the Partner Organisations 2014.

Full text of DOI:10.1039/c4ce00835a

View Article Online
View Journal
CrystEngComm
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: J. Hua, Y. Zhao,
Q. Liu, D. Zhao, K. Chen and W. Sun, CrystEngComm, 2014, DOI: 10.1039/C4CE00835A.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/crystengcomm

Page 1 of 32
CrystEngComm
View Article Online
DOI: 10.1039/C4CE00835A
Zinc(II) coordination polymers with substituted benzenedicarboxylate
and tripodal imidazole ligands: syntheses, structures and properties†
Ji-Ai Hua, Yue Zhao, Qing Liu, Dan Zhao, Kai Chen and Wei-Yin Sun*
Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of
Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures,
Nanjing University, Nanjing 210093, China. E-mail: sunwy@nju.edu.cn; Fax: +86 25
83314502
† Electronic supplementary information (ESI) available: Hydrogen bonding data for 2 - 4
(Table S1), nodes of building units in 1 and 2 (Fig. S1 and Fig. S2), 3D supramolecular
structures of 2 - 4 (Fig. S3), PXRD (Fig. S4) and TGA (Fig. S5). CCDC 993382 - 993385. For
ESI and crystallographic data in CIF or other electronic format see DOI:
By introducing 1,4-benzenedicarboxylic acid (H2BDC) with different substituent groups
H2BDC-R (R = NH2, OH, NO2) into Zn(II)-1,3,5-tris(1-imidazolyl)benzene (tib) system, four
new zinc(II) coordination polymers, namely [Zn5(tib)2(BDC-NH2)4(µ2-OH)2]·H2O (1),
[Zn2(tib)(BDC-NH2)SO4(H2O)2]·5H2O (2), [Zn2(tib)2(HBDC-OH)2(BDC-OH)]·2H2O (3) and
[Zn(tib)(BDC-NO2)]·H2O (4), have been successfully synthesized under solvothermal
conditions. Complexes 1 and 2 based on the same H2BDC-NH2 show different structures: 1 is
a 3-fold interpenetrated 3D framework with point (Schläfli) symbol {53·62·7}2{53}2{58·62·85},
while 2 exhibits a 2D network with {62·84}{62·8}4 topology. 3 and 4 are 2D networks with
different topologies of {63} and {44·62}, respectively. The structural diversity of 1-4 indicates
that the substituent groups of H2BDC as well as the reaction temperature and solvent play an
important role in determining the framework structures and topologies. Furthermore, the
sorption and photoluminescence properties of the complexes were investigated.
1

CrystEngComm
Page 2 of 32
View Article Online
DOI: 10.1039/C4CE00835A
Introduction
The rational design and syntheses of metal-organic frameworks (MOFs) have attracted great
attention of chemists not only because of their intriguing structural diversities and aesthetical
topologies but also due to their interesting properties and potential applications as functional
materials in gas storage/separation, heterogeneous catalysis, magnetism, photochemistry and
so on.1-5 Although much progress has been achieved in this field over the past years, it is still
a challenge for us to fabricate MOFs with fully predicted and/or controlled architectures and
properties.
From synthetic view, the MOFs structures could be controlled by appropriate organic
ligands and metal centers as well as reaction conditions like temperature, pH value, solvent
system and reactant stoichiometry.6-7 Among these, the organic ligand plays crucial role in the
construction of MOFs because of its characteristics such as geometric configuration,
rigidity/flexibility, functionality, length, symmetry and substituent group.8 Therefore,
changing organic ligand systematically is considered to be an effective way to investigate its
influence on construction of MOFs. In addition, in order to satisfy and mediate the geometric
requirement of metal centers, it is effective to adopt mixed-ligand strategy by incorporating
N-donor ligands and multicarboxylate as auxiliary linkers for the construction of MOFs.9 In
this regard, previous works have mainly focused on changing the substituent group of
carboxylate ligand.10 Systematic investigation has been carried out for IRMOF and MIL
series,11,12 which can be tuned in a systematic fashion without altering the underlying
topology by introducing functional groups such as -Br, -NH2, -CH3, -OH, -OC3H7, and -C2H4.
However, intensive exploration on the influence of substituent group in carboxylate ligands
on MOFs with versatile structures is still limited in mixed-ligand system.
Taking the above discussion into account, in this work we focus our attention on
2

Page 3 of 32
CrystEngComm
View Article Online
DOI: 10.1039/C4CE00835A
1,4-benzenedicarboxylic acid (H2BDC) with different substituent groups H2BDC-R (R = NH2,
OH, NO2) as auxiliary ligands to investigate the effect of substituent groups on the structures
of MOFs in Zn(II)-1,3,5-tris(1-imidazolyl)benzene (tib) system. Herein, four new Zn(II)
MOFs based on tib and auxiliary ligands H2BDC-R: [Zn5(tib)2(BDC-NH2)4(µ2-OH)2]·H2O (1),
[Zn2(tib)(BDC-NH2)SO4(H2O)2]·5H2O (2), [Zn2(tib)2(HBDC-OH)2(BDC-OH)]·2H2O (3) and
[Zn(tib)(BDC-NO2)]·H2O (4) have been synthesized under solvothermal conditions. All these
complexes were structurally characterized by single-crystal X-ray diffraction analyses, IR
spectroscopy, elemental analyses, powder X-ray diffraction (PXRD) and thermogravimetric
analyses (TGA). Moreover, sorption and photoluminescence properties of the complexes were
investigated.
Experimental
Materials and methods
All commercially available chemicals and solvents are of reagent grade and were used as
received without further purification. The tib ligand was synthesized according to the method
reported previously.13 Elemental analyses for C, H and N were performed on a Perkin-Elmer
240C Elemental Analyzer at the analysis center of Nanjing University. FT-IR spectra were
recorded in the range of 400 - 4000 cm-1 on a Bruker Vector22 FT-IR spectrophotometer using
KBr pellets. PXRD measurements were carried out on a Bruker D8 Advance X-ray
diffractometer using Cu-Kα radiation (λ = 1.5418 Å), in which the X-ray tube was operated at
40 kV and 40 mA. TGA were taken on a Mettler-Toledo (TGA/DSC1) thermal analyzer under
the N2 atmosphere with a heating rate of 10 ºC min-1. The luminescence spectra for the
powdered solid samples were measured on an Aminco Bowman Series 2 spectrofluorometer
with a xenon arc lamp as the light source. In the measurements of emission and excitation
spectra the pass width is 5 nm, and all the measurements were carried out under the same
3

CrystEngComm
Page 4 of 32
View Article Online
DOI: 10.1039/C4CE00835A
experimental conditions. Sorption experiments were carried out on a Belsorp-max volumetric
gas sorption instrument.
Preparation of [Zn5(tib)2(BDC-NH2)4(µ2-OH)2]·H2O (1). A mixture of tib (13.8 mg,
0.05 mmol), H2BDC-NH2 (9.0 mg, 0.05 mmol), ZnSO4·7H2O (28.8 mg, 0.1 mmol),
N,N-diethylformamide (DEF, 2 mL) and H2O (6 mL) was sealed in Teflon-lined stainless steel
container and heated at 150 ºC for 3 days. After being cooled to room temperature, yellow
block crystals of 1 were obtained in 42% yield. Anal. Calcd for C62H48N16O19Zn5: C, 45.18; H,
2.94; N, 13.60%. Found: C, 45.57; H, 3.02; N, 13.72%. IR (KBr pellet, cm-1): 3447 (m), 3136
(m), 2803 (w), 1627 (s), 1519 (s), 1436 (w), 1366 (w), 1321 (m), 1270 (m), 1124 (s), 1079
(m), 1016 (m), 946 (m), 863 (m), 761 (m), 682 (w), 646 (m), 610(m).
Preparation of [Zn2(tib)(BDC-NH2)SO4(H2O)2]·5H2O (2). A mixture of tib (13.8 mg,
0.05 mmol), H2BDC-NH2 (9.0 mg, 0.05 mmol), ZnSO4·7H2O (28.8 mg, 0.1 mmol),
N,N-dimethylformamide (DMF, 2 mL) and H2O (6 mL) was sealed in Teflon-lined stainless
steel container and heated at 85 ºC for 3 days. After being cooled to room temperature, yellow
crystals of 2 were obtained in 48% yield. Anal. Calcd for C23H31N7O15SZn2: C, 34.17; H, 3.87;
N, 12.13%. Found: C, 34.31; H, 3.72; N, 12.18%. IR (KBr pellet, cm-1): 3400 (m), 3142 (w),
1621 (s), 1576 (s), 1519 (s), 1387 (s), 1321 (m), 1296 (m), 1251 (m), 1156 (m), 1073 (s), 1019
(m), 952 (m), 857 (m), 807 (w), 762 (m), 672 (w), 655 (w), 602(m).
Preparation of [Zn2(tib)2(HBDC-OH)2(BDC-OH)]·2H2O (3). The complex 3 was
synthesized by the same procedure of 2, except that H2BDC-OH (9.0 mg, 0.05 mmol) was
used instead of H2BDC-NH2. After cooling to room temperature, colorless block crystals of 3
were obtained in 78% yield. Anal. Calcd for C54H42N12O17Zn2: C, 51.40; H, 3.36; N 13.32%.
Found: C, 51.65; H, 3.15; N, 13.12%. IR (KBr pellet, cm-1): 3466 (m), 3123 (m), 3052 (m),
1701(w), 1621 (s), 1516 (s), 1430 (s), 1379 (w), 1270 (m), 1220 (w), 1136 (m), 1079 (m),
1052 (w), 1019 (m), 974 (m), 952 (s), 896 (w), 845 (s), 761 (s), 685 (m), 651 (m), 617 (w).
4

Page 5 of 32
CrystEngComm
View Article Online
DOI: 10.1039/C4CE00835A
Preparation of [Zn(tib)(BDC-NO2)]·H2O (4). The title complex 4 was also obtained by
the same procedure of 2, except that H2BDC-NO2 (10.6 mg, 0.05 mmol) was used instead of
H2BDC-NH2. After cooling to room temperature, yellow block crystals of 4 were obtained in
59% yield. Anal. Calcd for C23H17N7O7Zn: C, 48.57; H, 3.01; N, 17.24%. Found: C, 48.38; H,
2.79; N, 17.34%. IR (KBr pellet, cm-1): 3416(m), 3104 (m), 3035 (w), 1614 (s), 1518 (s),
1404 (m), 1360 (s), 1277 (w), 1251(m), 1232 (m), 1124 (m), 1073 (s), 1022 (s), 939 (m), 889
(w), 870 (w), 828 (m), 799 (s), 742(m), 723 (m), 694 (m), 653 (s), 608 (w).
Crystallography
The crystallographic data collections for 1-4 were carried out on a Bruker Smart Apex II CCD
area-detector diffractometer with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å)
at 293(2) K using the ω-scan technique. The diffraction data were integrated by using the
SAINT program,14 which was also used for the intensity corrections for the Lorentz and
polarization effects. Semi-empirical absorption corrections were applied using SADABS
program.15 The structures were solved by direct methods and all the non-hydrogen atoms
were refined anisotropically on F2 by the full-matrix least-squares technique using the
SHELXL-97 crystallographic software package.16 The hydrogen atoms except those of water
molecules were generated geometrically and refined isotropically using the riding model. The
hydrogen atoms of water molecules in 2 and the ones of -OH and -COOH in 3 were found
from Fourier map directly while the ones of free water molecules in 1, 3 and 4 were not found.
The atoms Zn3, N7, N8 and N9 in 1 and O8 in 3 are disordered in two positions, each with
site occupancy of 0.50. The details of the crystal parameters, data collection, and refinements
for the complexes are summarized in Table 1 and selected bond lengths and angles are listed
in Table 2 and hydrogen bonding data for 2-4 are given in Table S1 (ESI†).
Results and discussion
5

CrystEngComm
Page 6 of 32
View Article Online
DOI: 10.1039/C4CE00835A
Crystal structure of [Zn5(tib)2(BDC-NH2)4(µ2-OH)2]·H2O (1)
Crystallographic analysis revealed that 1 crystallizes in triclinic space group P-1 and the
asymmetric unit of 1 contains half molecule of [Zn5(tib)2(BDC-NH2)4(µ2-OH)2]·H2O. There
are three different Zn(II) atoms and Zn3 is sitting on an inversion center but is disordered into
two positions each with a site occupancy of 0.50.17 The coordination environment of Zn(II) is
shown in Fig. 1a and it can be seen that Zn1 is four-coordinated by two carboxylate oxygen
(O1, O5) and two imidazole nitrogen atoms (N1, N3A) from two different BDC-NH2 and two
tib ligands, respectively, Zn2 atom also adopts a distorted tetrahedral coordination geometry
defined by two carboxylate oxygen atoms (O7, O3B) from two distinct BDC-NH2 and one
µ2-O atom (O9) shared with Zn3 and one imidazole nitrogen atom (N5) of tib ligand, while
Zn3 is six-coordinated with octahedral coordination geometry defined by four carboxylate
oxygen atoms (O8, O8C, O4B, O4D) from four different BDC-NH2 and two µ2-O (O9, O9C)
shared with two different Zn2 atoms. Zn2 and Zn3 are bridged by one µ2-OH and two
carboxylate groups with a Zn⋯Zn separation of 3.12 Å, and two Zn2 and one Zn3 form a
trinuclear subunit Zn3(OCO)4(µ2-OH)2. In 1, it is notable that BDC-NH2 presents three
different kinds of coordination modes as illustrated in Scheme 1a, 1b and 1c: one connects
two Zn(II) atoms with its carboxylate groups in (κ1)-(κ1)-ꢀ2-BDC-NH2 coordination mode
(Scheme 1a), another one in (κ1)-(κ1-κ1)-ꢀ3-BDC-NH2 mode (Scheme 1b), and the third one in
(κ1-κ1)-(κ1-κ1)-ꢀ4-BDC-NH2 bisbidentate coordination mode to connect four Zn(II) atoms
(Scheme 1c).18 Each tib ligand coordinates to three Zn(II) atoms. Tridentate tib and two kinds
of BDC-NH2 ligands with ꢀ2- and ꢀ4-bridging modes link the Zn(II) centers to form a
two-dimensional (2D) network (Fig. 1b), which is further connected together by the
BDC-NH2 with ꢀ3-bridging mode to form the final three-dimensional (3D) framework of 1
(Fig. 1c).
To further understand the structure of 1, topological analysis by reducing
6

Page 7 of 32
CrystEngComm
View Article Online
DOI: 10.1039/C4CE00835A
multidimensional structure to simple node-and-linker net was carried out. The above
mentioned Zn3(OCO)4(µ2-OH)2 subunit is surrounded by four BDC-NH2 and two tib ligands
and thus can be viewed as a six-connector (Fig. S1a), while Zn1 (Fig. S1b), tib and BDC-NH2
ligands can be considered as four-, three- and two-connector, respectively. According to the
simplification principle,19 the resulting structure of 1 is 3,4,6-connected 3-nodal 3D net with
stoichiometry (3-c)2(4-c)2(6-c) (Fig. 1d). Topological analysis by TOPOS program suggests
that the Point (Schläfli) symbol of the net is {53·62·7}2{53}2{58·62·85}. It is noteworthy that
there are large open channels (Fig. 1c), which allows another two identical nets to penetrate,
namely, the final structure of 1 is a 3-fold interpenetrated 3D framework (Fig. 1e).
Crystal structure of [Zn2(tib)(BDC-NH2)SO4(H2O)2]·5H2O (2)
As depicted in Fig. 2a, Zn1 in 2 is four coordinated by two imidazole nitrogen atoms (N3B,
N5A) from two distinct tib ligands, one carboxylate oxygen atom (O2) from one BDC-NH2
and one oxygen (O1W) from a coordinated water molecule to give a tetrahedral coordination
geometry, while Zn2 is six-coordinated with distorted octahedral coordination geometry by
two nitrogen atoms (N1, N7) from one tib ligand and one BDC-NH2 , two carboxylate oxygen
2-
(O3C, O4C) from one BDC-NH2 ligand and two oxygen ones (O6, O2W) from one SO4
anion and one coordinated water molecule. It is interesting to note that in 2 the nitrogen atom
of BDC-NH2 ligand participates in the coordination with Zn2, which is rare in the reported
MOFs.20 The BDC-NH2 ligand presents one kind of coordination mode (Scheme 1d), and
adopts a ꢀ3-bridging mode to connect three Zn(II) atoms with its carboxylate groups in
(κ1)-(κ2)-ꢀ2-BDC-NH2 coordination mode. Each tib coordinates with three Zn(II) atoms.
BDC-NH2 and tib ligands link the Zn(II) atoms to form a double-layered 2D network (Fig.
2b). Due to the coordination of nitrogen of BDC-NH2, a dinuclear subunit Zn2(BDC-NH2)2 is
formed by two BDC-NH2 and two Zn2, which can be regarded as a four-connected node (Fig.
S2), and each Zn1 by omitting terminal aqua ligand, tib and BDC-NH2 are viewed as three-,
7

CrystEngComm
Page 8 of 32
View Article Online
DOI: 10.1039/C4CE00835A
three- and two-connector, respectively. Accordingly, the 2D network of 2 can be simplified to
a (3,4)-connected 2-nodal net with stoichiometry (3-c)4(4-c), and its Point symbol is
{62·84}{62·8}4 (Fig. 2c). In addition, the adjacent 2D networks are further linked together by
hydrogen bonds to give a 3D supramolecular structure of 2 (Table S1 and Fig. S3a).
Crystal structure of [Zn2(tib)2(HBDC-OH)2(BDC-OH)]·2H2O (3)
When H2BDC-OH instead of H2BDC-NH2 was used in the reaction and the other reaction
conditions are the same as those used for the preparation of 2, complex 3 was obtained. It is
noteworthy that there are two different kinds of carboxylate ligands, namely BDC-OH and
HBDC-OH with complete and partial deprotonation of the carboxylate groups. As shown in
Fig. 3a, Zn(II) is four-coordinated with distorted tetrahedral coordination geometry by two
imidazole nitrogen atoms (N1, N3A) from two distinct tib ligands and two carboxylate
oxygen atoms (O1, O5) from one HBDC-OH and one BDC-OH. As illustrated in Scheme 1e
and 1f, BDC-OH and HBDC-OH act as ꢀ2-bridging and terminal ligands, respectively, the
BDC-OH with its carboxylate groups in (κ1)-(κ1)-ꢀ2-BDC-NH2 coordination mode and the
HBDC-OH in κ1-BDC-NH2 mode. In addition, one of three imidazole groups of tib ligand
does not take part in the coordination, and thus each tib ligand links two Zn(II) atoms. Such
connection mode makes 3 a 2D network structure (Fig. 3b). From topological view, 3 is a
3-connected uninodal net with a Point symbol of {63}, and 3-fold interpenetration occurred
due to the large voids of the 2D network (Fig. 3c). Furthermore, the adjacent 2D layers are
further connected together by hydrogen bonds to form a 3D supramolecular architecture
(Table S1 and Fig. S3b).
Crystal structure of [Zn(tib)(BDC-NO2)]·H2O (4)
When H2BDC-NO2 was used as the auxiliary ligand, complex 4 was isolated. The asymmetric
unit of 4 contains one Zn(II), one tib, one BDC-NO2 and one lattice water molecule. Zn1 also
adopts a distorted tetrahedral coordination geometry with two imidazole nitrogen atoms (N1,
8

Page 9 of 32
CrystEngComm
View Article Online
DOI: 10.1039/C4CE00835A
N3B) from two tib and two carboxylate oxygen atoms (O1, O4A) from two BDC-NO2 ligands
(Fig. 4a). The tib ligand in 4 acts as a two-connector with one imidazole group free of
coordination as that in 3, and each tib links two Zn(II) atoms to form a one-dimensional (1D)
chain, and then BDC-NO2 adopts a ꢀ2-bridging mode with its carboxylate groups in
(κ1)-(κ1)-ꢀ2-BDC-NH2 coordination mode (Scheme 1g) and connects the 1D chains to give a
2D network (Fig. 4b). The 2D network of 4 can be simplified to a 4-connected uninodal net,
and its Point symbol is {44.62} (Fig. 4c). In addition, the adjacent 2D networks are further
linked by hydrogen bonds to form a 3D supramolecular framework of 4 (Table S1 and Fig.
S3c).
Effect of the reaction conditions and substituent group of the auxiliary ligand on
structures of the complexes
In the present study, 1 and 2 were obtained by using the same auxiliary ligand H2BDC-NH2
but under different reaction solvent and temperature, as a result, 1 is 3-fold interpenetrating
3D structure, while 2 displays a 2D network. The different structures of 1 and 2 may be
ascribed to the different basicity of (CH3CH2)2NH and (CH3)2NH generated in situ by
decomposition of solvent DEF and DMF, respectively, as reflected by the presence of µ2-OH
groups in 1 but no ones in 2. In addition, reaction temperature for preparation of 1 is higher
than that for 2, which may be needed for release of (CH3CH2)2NH from DEF. When the
reaction for preparation of 1 was carried out 85 ºC, instead of 150 ºC, yellow block crystals of
Zn(II)-tib without H2BDC-NH2 was obtained.21 In addition, when the reaction for synthesis of
2 was performed at 150 ºC, only amorphous powders were obtained. The results imply that
reaction solvent and temperature are important for formation of 1 and 2. Furthermore, as
observed in 1 and 2 as well in the previously reported MOFs,22 the higher reaction
temperature results MOFs with high density and high dimensionality, but less coordinated and
non-coordinated solvent/water molecules. As for 2, 3 and 4 obtained under the same reaction
9

CrystEngComm
Page 10 of 32
View Article Online
DOI: 10.1039/C4CE00835A
conditions, it can be seen the influence of the substituent groups of the H2BDC on the
structures of MOFs.23 They are 2D networks, however, their structures and topologies are
distinct remarkably. It is interesting to note that the previously reported MOFs with BDC-R
(R = NH2, Br, Cl, NO2, OH etc.) have the same framework structure and topology, but
different pore size and functionality.11,12 The different structures of 2, 3 and 4 imply that an
approach toward tuning structural diversity of MOFs can be realized by modifying the
substituent groups in the auxiliary carboxylate ligands.23
Powder X-ray diffraction (PXRD) and thermal stability
The pure phase of 1 - 4 was confirmed by PXRD measurements and each PXRD pattern of
the as-synthesized sample is consistent with the simulated one, indicating the phase purity of
the products (Fig. S4).
The thermal stability of 1-4 was examined by thermogravimetric analysis (TGA) and the
results are shown in Fig. S5a. Complex 1 loses 1.21% of weight in the temperature range of
30-130 °C, which is attributed to the departure of the free water molecules (calcd 1.09%), and
the residue can stable up to about 300 °C. For 2, an obvious weight loss was found before
150 °C due to the liberation of free and coordinated water molecules with a weight loss of
15.25% (calcd 15.55%), which are in agreement with the results of its crystal structure, and
the residue is stable up to about 340 °C. Complex 3 shows a weight loss of 3.03% in the
temperature range of 150-220 °C corresponding to the release of the free water molecules
(calcd 2.85%), and the decomposition of the residue was observed at about 340 °C. For 4, the
TGA curve displays a weight losses of 3.03%, suggesting the loss of the free water molecules
(calcd 3.16%), and the framework of 4 is stable up to about 380 °C.
The desolvated samples 1′-4′ were obtained by heating the fresh complexes 1-4 at
corresponding temperature for 10 h under high vacuum, respectively, as shown in Fig. S5b.
The results confirm the complete removal of free water molecules in 1, 3 and 4. While 2′ still
10

Page 11 of 32
CrystEngComm
View Article Online
DOI: 10.1039/C4CE00835A
shows a weight loss of 2.46%, which may be ascribed to the loss of one of the two
coordinated water molecules (calcd 2.57%). From crystal structural analysis, it can be seen
that the coordinated water molecule O1W has a shorter bond length of 2.011(3) Å than that of
O2W of 2.206(3) Å and strong hydrogen bonds as listed in Table S1. The PXRD patterns of
dehydrated samples confirm that they have good crystallinity. The results of PXRD imply that
1-4 have good stability and the desolvated samples 1′-4′ have the framework structures
without collapses.
Sorption property
Given the stability of the frameworks ascertained by PXRD (Fig. S4) and TGA (Fig. S5b), in
addition, the crystallographic values of the void space calculated with Platon for the four
compounds are 5.6%, 21.1%, 5.4%, 3.1%, respectively, vapour sorption of 1′-4′ were
investigated. As shown in Fig. 5a, the H2O vapour adsorption isotherm at 298 K of 1′ shows
gradual uptake with a final value of 1.53 mol mol-1 at P = 1.03 atm, which is a little larger
than the experimental value of 1.0 indicated by crystallographic analysis. The uptake of
MeOH and EtOH is 1.28 mol mol-1 at P = 0.99 atm and 0.33 mol mol-1 at P = 0.90 atm,
respectively. The desorption profiles of H2O, MeOH and EtOH do not retrace the adsorption
one with a large hysteresis loop. This phenomenon may be ascribed to the strong
adsorbate-adsorbent interactions, in addition the reorganization of 1 during the loss and
uptake of solvent molecules and adsorbate-adsorbate interactions also play an important
role.24
The H2O, MeOH and EtOH vapour adsorption isotherms of 2′ exhibit similar type I-like
profiles and desorption profiles coincide well with the adsorption curves (Fig. 5b). The final
uptake value of H2O, MeOH and EtOH is 6.85, 3.12 and 1.34 mol mol-1 at P = 0.90 atm,
respectively. The H2O sorption amount is larger than the calculated value of 6.0 indicated by
the TGA of desolvated samples 2′, which may be attributed to the extension of the layered
11

CrystEngComm
Page 12 of 32
View Article Online
DOI: 10.1039/C4CE00835A
structure.25
From the adsorption isotherm of 3′, it can be seen that only uptake H2O and MeOH were
observed but no EtOH at 298 K (Fig. 5c) and the adsorption of MeOH isotherm exhibits an
interesting phenomenon: up to P = 0.4 atm, nearly no adsorption is found, but after that the
uptake rapidly increases to 1.91 mol mol-1 at P = 0.57 atm and gradually reaches the
maximum value 2.87 mol mol-1 at P = 0.93 atm. It can be considered to be type V. Such
unusual phenomenon of isotherms is typical for flexible, so-called “gate pressure” MOFs.26
The final value of the H2O uptake is 3.80 mol mol-1 at P = 0.90 atm, which is larger than the
experimental value (2.0) from the crystal structure. It is may be due to the extension of the
layered structure and the water-framework interactions between the -OH groups and adsorbed
water molecules. 25,12a
The H2O, MeOH and EtOH vapour adsorption isotherms of 4′ are shown in Fig. 5d. The
H2O vapour adsorption isotherm is similar to that of 2′ and is of type I behavior with small
hysteresis and the final saturated uptake volume of H2O is 2.16 mol mol-1 at P = 0.87 atm.
And the EtOH adsorption isotherm is similar to MeOH adsorption of 3′ and the final saturated
uptake is 1.00 mol mol-1 at P = 0.90 atm. However, the MeOH adsorption profiles undergo a
distinct two-step curves with two abrupt jumps at p ~ 0.14 and 0.48 atm, and gradually
reaches a saturation uptake of 2.81 mol mol-1 at 0.86 atm with notable hysteresis, thus, it can
be classified as type VI-like profiles. The similar phenomenon was also reported for a number
of flexible MOFs, which could be resulted from the flexible frameworks and the interaction
between the framework and the guest or diffusion barrier.27 The large hysteresis and stepwise
process of MeOH adsorption profiles of 4′ is characteristic of the dynamic of flexible MOFs.28
Moreover, the MeOH adsorption isotherm of 4′ can be attributed to “gate-open behavior”.
This has also been previously observed during the high-pressure CO2 sorption analysis of
29c
M-MIL-53 (M = Al or Cr)29a,29b or Al-MIL-53-NH2
and can be interpreted into the
12

Page 13 of 32
CrystEngComm
View Article Online
DOI: 10.1039/C4CE00835A
following hypothesis: after the adsorption of the first portion of MeOH molecules, the
degassed solid remains similar to the hydrated complex. At higher vapor pressures, the
framework opens up and takes up additional MeOH molecules into the framework.
Comparing the sorption properties of these four desolvated samples, except for 1′, the
H2O desorption profiles of 2′-4′ display incomplete desorption, which may be attributed to the
strong adsorbate-adsorbent interactions such as hydrogen bonds.26 In addition, it can be seen
that 2′ has advantages over the other three complexes in selective H2O adsorption, while 4′
has superiority in selective MeOH adsorption. The results show their potential applications as
late-model water and MeOH absorbents in the field of adsorption materials.
Photoluminescence properties
Considering metal complexes with d10 metal centers and conjugated organic linkers are
promising candidates for the hybrid photoactive materials with potential application such as
light-emitting diodes (LEDs),30 the solid-state luminescent emission spectra of 1-4 as well as
free tib ligands were investigated at ambient temperature. Since 1-4 are stable in air and
insoluble in water or most organic solvents, no measurements in solution were performed.31
Intense emission band was observed at 405 nm for the free tib with excitation at 360 nm. 32 As
shown in Fig. 6, emission bands were observed at 430 nm (λex = 368 nm) for 1, 434 nm (λex =
366 nm) for 2, 435 nm (λex = 348 nm) for 3, 430 nm (λex = 360 nm) for 4. The emissions of
1-4 are tentatively attributed to the tib ligands,32-34 since the emission bands of the carboxylate
ligands are usually weak compared to that of tib, and it was considered that the carboxylate
ligands have no significant contribution to the fluorescence emission of 1-4 with the presence
of the N-donor ligand.35 The red-shifted emissions of 1-4 are considered to be caused by the
coordination of the ligands to the metal centers.36-38
Conclusion
13

CrystEngComm
Page 14 of 32
View Article Online
DOI: 10.1039/C4CE00835A
In conclusion, four new Zn(II) MOFs constructed from tripodal imidazole-containing ligand
1,3,5-tris(1-imidazolyl)benzene and 1,4-benzenedicarboxylic acid with different substituent
groups were successfully obtained under solvothermal conditions. The complexes display
versatile 2D and 3D frameworks. The results showed that the factors such as substituent
groups as well as reaction temperature and solvent have remarkable impact on the structure of
the MOFs in this system. In addition, the linear rigid H2BDC-R ligand was further proven to
be a good candidate for constructing novel architectures, which would provide promising
access to the design and synthesis of MOFs with novel structures and properties.
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China
(Grant no. 21331002 and 91122001) and the National Basic Research Program of China
(Grant no. 2010CB923303).
References
1
(a) M. O’Keeffe and O. M. Yaghi, Chem. Rev., 2012, 112, 675; (b) Q.-X. Yang, X.-Q.
Chen, Z.-J. Chen, Y. Hao, Y.-Z. Li, Q.-Y. Lu and H.-G. Zheng, Chem. Commun., 2012,
48, 10016; (c) F. Guo, F. Wang, H. Yang, X.-L. Zhang and J. Zhang, Inorg. Chem., 2012,
51, 9677.
2
(a) J. R. Li, R. J. Kuppler and H.-C. Zhou, Chem. Soc. Rev., 2009, 38, 1477; (b) H.
Uehara, S. Diring, S. Furukawa, Z. Kalay, M. Tsotsalas, M. Nakahama, K. Hirai, M.
Kondo, O. Sakata and S. Kitagawa, J. Am. Chem. Soc., 2011, 133, 11932; (c) Y. Kang, F.
Wang, J. Zhang and X.-H. Bu, J. Am. Chem. Soc., 2012, 134, 17881; (d) J.-P. Zhang,
Y.-B. Zhang, J.-B. Lin and X.-M. Chen, Chem. Rev., 2012, 112, 1001.
3
(a) C.-D. Wu, A.-G. Hu, L. Zhang and W.-B. Lin, J. Am. Chem. Soc., 2005, 127, 8940; (b)
14

Page 15 of 32
CrystEngComm
View Article Online
DOI: 10.1039/C4CE00835A
L.-Q. Ma, C. Abney and W.-B. Lin, Chem. Soc. Rev., 2009, 38, 1248; (c) J. Lee, O. K.
Farha, J. Roberts, K. A. Scheidt, S. T. Nguyen and J. T. Hupp, Chem. Soc. Rev., 2009, 38,
1450; (d) F.-J. Song, C. Wang, J. M. Falkowski, L.-Q. Ma and W.-B. Lin, J. Am. Chem.
Soc., 2010, 132, 15390; (e) Y. Zhao, X. Zhou, T. Okamura, M. Chen, Y. Lu, W.-Y. Sun
and J.-Q. Yu, Dalton Trans., 2012, 41, 5889; (f) Y. Zhao, K. Chen, J. Fan, T. Okamura,
Y. Lu, L. Luo and W.-Y. Sun, Dalton Trans., 2014, 43, 2252.
4
(a) Y.-F. Zeng, X. Hu, F.-C. Liu and X.-H. Bu, Chem. Soc. Rev., 2009, 38, 469; (b) H.-L.
Wang, D.-P. Zhang, D.-F. Sun, Y.-T. Chen, K. Wang, Z.-H. Ni, L.-J. Tian and J.-Z. Jiang,
CrystEngComm., 2010, 12, 1096; (c) S.-Y. Qian, H. Zhou, A. H. Yuan and Y. Song,
Cryst. Growth Des., 2011, 11, 5676; (d) L.-H. Jia, R.-Y. Li, Z.-M. Duan, S.-D. Jiang,
B.-W. Wang, Z.-M. Wang and S. Gao, Inorg. Chem., 2011, 50, 144.
5
(a) V. W-W. Yam and K. K-W. Lo, Chem. Soc. Rev., 1999, 28, 323; (b) M. M.
Wanderley, C. Wang, C.-D. Wu and W.-B. Lin, J. Am. Chem. Soc., 2012, 134, 9050; (c)
L.-L. Zhang, F.-L. Liu, Y. Guo, X.-P. Wang, J. Guo, Y.-H. Wei, Z. Chen and D.-F. Sun,
Cryst. Growth Des., 2012, 12, 6215; (d) J.-S. Hu, X.-Q. Yao, M.-D. Zhang, L. Qin, Y.-Z.
Li, Z.-J. Guo, H.-G. Zheng and Z.-L. Xue, Cryst. Growth Des., 2012, 12, 3426; (e) L.
Luo, K. Chen, Q. Liu, Y. Lu, T. Okamura, G.-C. Lv, Y. Zhao and W.-Y. Sun, Cryst.
Growth Des., 2013, 13, 2312.
6
(a) S. L. James, Chem. Soc. Rev., 2003, 32, 276; (b) R. Custelcean and M. G. Gorbunova,
J. Am. Chem. Soc., 2005, 127, 16362; (c) K. Yu, B.-B. Zhou, Y. Yu, Z.-H. Su, Y. Wang,
C.-M. Wang and C.-X. Wang, Dalton Trans., 2012, 41, 10014; (d) Y. Zhao, L.-L. Zhai, J.
Fan, K. Chen and W.-Y. Sun, Polyhedron., 2012, 46, 16; (e) Y. Zhao, L.-L. Zhai, G.-C.
Lv, X. Zhou and W.-Y. Sun, Inorg. Chim. Acta., 2012, 392, 38; (f) Y. Zhang, B.-B. Guo,
L. Li, S.-F. Liu and G. Li, Cryst. Growth Des., 2013, 13, 367.
7
(a) X.-Y. Wang, L. Wang, Z.-M. Wang and S. Gao, J. Am. Chem. Soc., 2006, 128, 674;
15

CrystEngComm
Page 16 of 32
View Article Online
DOI: 10.1039/C4CE00835A
(b) C.-F. Zhuang, J. Zhang, Q. Wang, Z.-H. Chu, D. Fenske and C.-Y. Su, Chem.-Eur. J.,
2009, 15, 7578; (c) S.-M. Fang, Q. Zhang, M. Hu, E. C. Sanudo, M. Du and C.-S. Liu,
Inorg. Chem., 2010, 49, 9617; (d) M. Chen, S.-S. Chen, T. Okamura, Z. Su, M.-S. Chen,
Y. Zhao, W.-Y. Sun and N. Ueyama, Cryst. Growth Des., 2011, 11, 1901; (e) L. Wang,
Z.-H. Yan, Z.-Y. Xiao, D. Guo, W.-Q. Wang and Y. Yang, CrystEngComm., 2013, 15,
5552.
8
9
(a) C. Pettinari, N. Masciocchi, L. Pandolfo and D. Pucci, Chem.-Eur. J., 2010, 16, 1106;
(b) J.-P. Zhang, Y.-B. Zhang, J.-B. Lin and X.-M. Chen, Chem. Rev., 2012, 112, 1001.
(a) Z. Su, J. Xu, J. Fan, D.-J. Liu, Q. Chu, M.-S. Chen, S.-S. Chen, G.-X. Liu, X.-F.
Wang and W.-Y. Sun, Cryst. Growth Des., 2009, 9, 2801; (b) Z. Su, J. Fan, T. Okamura,
M.-S. Chen, S.-S. Chen, W.-Y. Sun and N. Ueyama, Cryst. Growth Des., 2010, 10, 1911;
(c) Y. Zhao, M.-F. Lv, J. Fan, L. Luo, Z. Su and W.-Y. Sun, Inorg. Chim. Acta., 2011,
377, 138; (d) Y. Liu, N. Li, L. Li, H.-L.Guo, X.-F. Wang and Z.-X. Li, CrystEngComm.,
2012,14, 2080.
10 (a) K. Jiang, L.-F. Ma, X.-Y. Sun and L.-Y. Wang, CrystEngComm., 2011, 13, 330; (b)
L.-F. Ma, M.-L. Han, J.-H. Qin, L.-Y. Wang and M. Du, Inorg. Chem., 2012, 51, 9431; (c)
H.-J. Cheng, H.-X. Li, Z.-G. Ren, C.-N. Lü, J. Sh and J.-P. Lang, CrystEngComm., 2012,
14, 6064.
11 M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O’Keeffe and O. M. Yaghi,
Science, 2002, 295, 469.
12 (a) S. Biswas, T. Ahnfeldt and N. Stock, Inorg. Chem., 2011, 50, 9518; (b) S. Biswas, D.
E. P. Vanpoucke, T. Verstraelen, M. Vandichel, S. Couck, K. Leus, Y.-Y. Liu, M.
Waroquier, V. V. Speybroeck, J. F. M. Denayer and P. V. D. Voort, J. Phys. Chem. C.,
2013, 117, 22784.
13 (a) W. Zhao, Y. Song, T. Okamura, J. Fan, W.-Y. Sun and N. Ueyama, Inorg. Chem.,
16

Page 17 of 32
CrystEngComm
View Article Online
DOI: 10.1039/C4CE00835A
2005, 44, 3330; (b) J. Fan, W.-Y. Sun, T. Okamura, W.-X. Tang and N. Ueyama, Inorg.
Chem., 2003, 42, 3168.
14 SAINT, Program for Data Extraction and Reduction; Bruker AXS, Inc.: Madison, WI,
2001.
15 G. M. Sheldrick, SADABS; University of Göttingen: Göttingen, Germany.
16 G. M. Sheldrick, SHELXS-97, Program for the Crystal Structure Solution; University of
Göttingen: Göttingen, Germany, 1997.
17 (a) A. Choudhury, S. Natarajan and C. N. R. Rao, Inorg. Chem., 2000, 39, 4295; (b) Y.
Gong, J. Li, J.-B Qin, T. Wu, R. Cao and J.-H. Li, Cryst. Growth Des., 2011, 11, 1662; (c)
F.-L. Hu, W. Wu, P. Liang, Y.-Q. Gu, L.-G. Zhu, H. Wei and J.-P. Lang, Cryst. Growth
Des., 2013, 13, 5050; (d) J. H. Park, W. R. Lee, Y. Kim, H. J. Lee, D. W. Ryu, W. J.
Phang and C. S. Hong, Cryst. Growth Des., 2014, 14, 699.
18 W. Huang, D. Wu, P. Zhou, W. Yan, D. Guo, C. Duan and Q. Meng, Cryst. Growth Des.,
2009, 9, 1361.
19 (a) V. A. Blatov, IUCr CompComm Newsletter, 2006, 7, 4; (b) V. A. Blatov, TOPOS, A
Multipurpose Crystallochemical Analysis with the Program Package; Samara State
University, Russia, 2009.
20 F.-J. Liu, D. Sun, H.-J. Hao, R.-B. Huang and L.-S. Zheng, Cryst. Cryst. Growth Des.,
2012, 12, 354.
21 Z. Su, Z.-B. Wang, W.-Y. Sun, Inorg. Chem. Commun., 2010, 13, 1278.
22 (a) T.R. Jensen, N. Gérentes, J. Jepsen, R.G. Hazell and H.J. Jakobsen, Inorg. Chem.,
2005, 658; (b) P. Wang, L. Luo, J. Fan, G.-C. Lv, Y. Song and W.-Y. Sun, Micropor.
Mesopor. Mater., 2013, 175, 116; (c) Z.-H. Chen, Y. Zhao, S.-S. Chen, P. Wang and
W.-Y. Sun, J. Solid State Chem., 2013, 202, 215.
23 (a) M. Du, Z.-H. Zhang, Y.-P. You and X.-J. Zhao, CrystEngComm., 2008, 10, 306; (b)
17

CrystEngComm
Page 18 of 32
View Article Online
DOI: 10.1039/C4CE00835A
C.-P. Li, Q. Yu, Z.-H. Zhang and M. Du, CrystEngComm., 2010, 12, 834; (c) C.-P. Li, J.
Chen, Q. Yu and M. Du, Cryst. Growth Des., 2010, 10, 1623; (d) F. Guo, B.-Y. Zhu,
M.-L. Liu, X.-L. Zhang, J. Zhang and J.-P. Zhao, CrystEngComm., 2013,15, 6191.
24 (a) C. E. Webster, R. S. Drago and M. C. Zerner, J. Am. Chem. Soc., 1998, 120, 5509; (b)
R. F. de Luis, M. K. Urtiaga, J. L. Mesa, A. T. Aguayo, T. Rojob and M. I. Arriortua,
CrystEngComm., 2010, 12, 1880; (c) S. Bureekaew, H. Sato, R. Matsuda, Y. Kubota, R.
Hirose, J. Kim, K. Kato, M. Takata and S. Kitagawa, Angew. Chem., Int. Ed., 2010, 49,
7660.
25 (a) T. KumarMaji, K. Uemura, H.-C. Chang, R. Matsuda and S. Kitagawa, Angew. Chem.,
Int. Ed., 2004, 43, 3269; (b) A. Kondo, A. Chinen, H. Kajiro, T. Nakagawa, K. Kato, M.
Takata, Y. Hattori, F. Okino, T. Ohba, K. Kaneko and H. Kanoh, Chem.-Eur. J., 2009, 15,
7549; (c) J. Seo, R. Matsuda, H. Sakamoto, C. Bonneau and S. Kitagawa, J. Am. Chem.
Soc., 2009, 131, 12792; (d) S. Henke, A. Schneemann, A. Wutscher and R. A. Fischer, J.
Am. Chem. Soc., 2012, 134, 9464.
26 (a) M. K. Sharma, I. Senkovska, S. Kaskel, and P. K. Bharadwaj, Inorg. Chem., 2011, 50,
539; (b) C. Hou, Q. Liu, Y. Lu, T. Okamura, P. Wang, M. Chen and W.-Y. Sun,
Micropor. Mesopor. Mater., 2012, 152, 96; (c) C. Hou, Q. Liu, Y. Lu, T. Okamura, P.
Wang and W.-Y. Sun, CrystEngComm., 2012, 14, 8569.
27 (a) M. Eddaoudi, H.-L. Li and O. M. Yaghi, J. Am. Chem. Soc., 2000, 122, 1391; (b) T. K.
Maji, K. Uemura, H. C. Chang, R. Matsuda and S. Kitagawa, Angew. Chem., Int. Ed.,
2004, 43, 3269; (c) A.-X. Zhu, R.-B. Lin, Y. Liu, Y.-Y. Lin, J.-P. Zhang and X.-M. Chen,
Micropor. Mesopor. Mater., 2012, 157, 42; (d) A. Shigematsu, T. Yamada and H.
Kitagawa, J. Am. Chem. Soc., 2012, 134, 13145; (e) K. Zhang, R. P. Lively, M. E. Dose,
A. J. Brown, C. Zhang, J. Chung, S. Nair, W. J. Korosa and R. R. Chance, Chem.
Commun., 2013, 49, 3245; (f) L.-Q. Han, Y. Yan, F.-X. Sun, K. Cai, T. Borjigin, X.-J.
18

Page 19 of 32
CrystEngComm
View Article Online
DOI: 10.1039/C4CE00835A
Zhao, F.-Y. Qu and G.-S. Zhu, Cryst. Growth Des., 2013, 13, 1458.
28 (a) R. Kitaura, K. Fujimoto, S. Noro, M. Kondo and S. Kitagawa, Angew. Chem., Int. Ed.,
2002, 41, 133; (b) N. Yanai, W. Kaneko, K. Yoneda, M. Ohba and S. Kitagawa, J. Am.
Chem. Soc., 2007, 129, 3496; (c) A. Hazra, P. Kanoo, G. Mostafab and T. K. Maji,
CrystEngComm., 2010, 12, 2775; (d) M. K. Sharma, I. Senkovska, S. Kaskel and P. K.
Bharadwaj, Inorg. Chem., 2011, 50, 539.
29 (a) C. Serre, S. Bourrelly, A. Vimont, N. A. Ramsahye, G. Maurin, P. L. Llewellyn, M.
Daturi, Y. Filinchuk, O. Leynaud, P. Barnes and G. Férey, Adv. Mater., 2007, 19, 2246;
(b) S. Bourrelly, P. L. Llewellyn, C. Serre, F. Millange, T. Loiseau and G. Férey, J. Am.
Chem. Soc., 2005, 127, 13519; (c) S. Couck, J. F. M. Denayer, G. V. Baron, T. Rémy, J.
Gascon and F. Kapteijn, J. Am. Chem. Soc., 2009, 131, 6326.
30 (a) F. Würthner and A. Sautter, Chem. Commun., 2000, 445; (b) D. M. Ciurtin, N. G
Pschirer, M. D. Smith, U. H. F. Bunz and H. C. Loye, Chem. Mater., 2001, 13, 2743; (c)
C. S. B. Gomes, P. T. Gomes, M. T. Duarte, R. E. DiPaolo, A. L. Macanita and M. J.
Calhorda, Inorg. Chem., 2009, 48, 11176; (d) L.-P. Zhang, J.-F. Ma, J. Yang, Y.-Y. Pang
and J.-C. Ma, Inorg. Chem., 2010, 49, 1535.
31 (a) H.-Y. Wang, S. Gao, L.-H. Huo, S.-W. Ng and J.-G. Zhao, Cryst. Growth Des., 2008,
8, 665; (b) M.-X. Li, Z.-X. Miao, M. Shao, S.-W. Liang and S.-R. Zhu, Inorg. Chem.,
2008, 47, 4481; (c) M. D. Allendorf, C. A. Bauer, R. K. Bhakta and R. J. T. Houk, Chem.
Soc. Rev., 2009, 38, 1330; (d) H. Ren, T.-Y. Song, J.-N. Xu, S.-B. Jing, Y. Yu, P. Zhang
and L.-R. Zhang, Cryst. Growth Des., 2009, 9, 105.
32 (a) L. Li, J. Fan, T. Okamura, Y.-Z. Li, W.-Y. Sun and N. Ueyama, Supramol. Chem.,
2004, 16, 361; (b) G.-H. Wei, J. Yang, J.-F. Ma, Y.-Y. Liu, S.-L. Li and L.-P. Zhang,
Dalton Trans., 2008, 3080; (c) X.-L. Wang, Y.-F. Bi, G.-C. Liu, H.-Y. Lin, T.-L. Hu and
X.-H. Bu, CrystEngComm., 2008, 10, 349; (d) K. O. Ashiry, Y.-H. Zhao, K.-Z. Shao,
19

CrystEngComm
Page 20 of 32
View Article Online
DOI: 10.1039/C4CE00835A
Z.-M. Su and G.-J. Xu, Polyhedron., 2009, 28, 975; (e) L. Zhang, Z.-J. Li, Q.-P. Lin,
Y.-Y. Qin, J. Zhang, P.-X. Yin, J.-K. Cheng and Y.-G. Yao, Inorg. Chem., 2009, 48,
6517.
33 (a) L.-L.Wen, Z.-D. Lu, J.-G. Lin, Z.-F. Tian, H.-Z. Zhu and Q.-J. Meng, Cryst. Growth
Des., 2007, 7, 93; (b) J.-G. Lin, S.-Q. Zang, Z.-F. Tian, Y.-Z. Li, Y.-Y. Xu, H.-Z. Zhu
and Q.-J. Meng, CrystEngComm., 2007, 9, 915; (c) H.-S. Liu, Y.-Q. Lan and S.-L. Li,
Cryst. Growth Des., 2010, 10, 5221;(d) L. Chen, L. Zhang, S.-L. Li, Y.-Q. Qiu, K.-Z.
Shao, X.-L. Wan and Z.-M. Su, CrystEngComm., 2013, 15, 8214.
34 (a) G. R. Choppin and D. R. Peterman, Coord. Chem. Rev., 1998, 174, 283; (b) V. W. W.
Yam and K. K. W. Lo, Chem. Soc. Rev., 1999, 28, 323; (c) X.-L. Wang, C. Qin, E.-B.
Wang and Z.-M. Su, Chem.-Eur. J., 2006, 12, 2680.
35 Y.-W. Li, H. Ma, Y.-Q. Chen, K.-H. He, Z.-X. Li and X.-H. Bu, Cryst. Growth Des.,
2012, 12, 189.
36 (a) G.-B. Che, C.-B. Liu, B. Liu, Q.-W. Wang and Z.-L. Xu, CrystEngComm, 2008, 10,
184; (b) M. D. Allendorf, C. A. Bauer, R. K. Bhakta and R. J. T. Houk, Chem Soc. Rev.,
2009, 38, 1330; (c) L. Zhang, Z.-J. Li, Q.-P. Lin, Y.-Y. Qin, J. Zhang, P.-X. Yin, J.-K.
Cheng and Y.-G. Yao, Inorg. Chem., 2009, 48, 6517.
37 (a) R. B. Fu, S. C. Xiang, S. M. Hu, L. S. Wang, Y. M. Li, X. H. Huang and X. T. Wu,
Chem. Commun., 2005, 5292; (b) Y.-Q. Huang, B. Ding, H.-B. Song, B. Zhao, P. Ren, P.
Cheng, H.-G. Wang, D.-Z. Liao and S.-P. Yan, Chem. Commun., 2006, 4906; (c) G.-Z.
Liu, S.-H. Li, X.-L. Li, L.-Y. Xin and L.-Y. Wang, CrystEngComm., 2013, 15, 4571.
38 (a) M. D. Allendorf, C. A. Bauer, R. K. Bhakta and R. J. T. Houk, Chem. Soc. Rev., 2009,
38, 1330; (b) C.-P. Li and M. Du, Chem. Commun., 2011, 47, 5958; (c) Y.-J. Cui, Y.-F.
Yue, G.-D. Qian and B.-L. Chen, Chem. Rev., 2012, 112, 1126.
20

Page 21 of 32
CrystEngComm
View Article Online
DOI: 10.1039/C4CE00835A
Table 1 Crystal Data and Structure Refinements for Complexes 1-4.
1
2
3
4
Empirical formula
Formula weight
Crystal system
Space group
a /Å
C62H48N16O19Zn5 C23H31N7O15SZn2 C54H42N12O17Zn2 C23H17N7O7Zn
1648.01
Triclinic
P-1
808.35
Triclinic
P-1
1261.74
Monoclinic
P21/c
568.81
Monoclinic
P21/n
11.539(3)
11.562(3)
14.283(3)
99.419(3)
96.191(3)
117.938(3)
1623.2(6)
1
7.999(10)
11.703(5)
17.386(2)
104.387(2)
98.557(2)
96.306(2)
1540.5(3)
2
14.6517(16)
7.8277(8)
22.551(2)
90
10.426(5)
18.990(10)
11.711(6)
90
b /Å
c /Å
α /°
β /°
90.01(2)
90
96.875(10)
90
γ /°
V /Å3
2586.4(5)
2
2302.0(2)
4
Z
Dc /g cm-3
ꢀ /mm-1
1.686
1.743
1.620
1.641
1.908
1.709
1.017
1.129
F(000)
834
828
1292
1160
Reflections
collected
Unique reflections
Goodness-of-fit
11637
8655
18763
13137
5614
5409
5082
4285
1.019
0.0663
1.034
0.0368
0.0975
1.075
0.0393
0.1150
1.039
0.0297
a
R1 [I > 2σ (I)]
b
wR2 [I > 2σ (I)]
0.1852
0.0829
a
b
2
R1 =Σ||Fo| - |Fc||/Σ|Fo|. wR2 = |Σw(|Fo|2 - |Fc|2)|/Σ|w(Fo)2|1/2, where w = 1/[σ2(Fo ) + (aP)2 +
2
bP]. P = (Fo + 2Fc2)/3.
21

CrystEngComm
Page 22 of 32
View Article Online
DOI: 10.1039/C4CE00835A
Table 2 Selected Bond Lengths (Å) and Angles (deg) for Complexes 1-4 a.
1
Zn(1)-O(5)
1.934(4)
1.962(5)
1.943(4)
1.927(6)
1.918(4)
2.207(5)
2.141(6)
106.6(2)
104.9(2)
127.1(2)
112.4(2)
120.2(2)
104.23(19)
157.96(8)
160.61(7)
87.68(19)
103.1(2)
Zn(1)-N(1)
2.033(5)
Zn(1)-O(1)
Zn(1)-N(3)#1
2.001(5)
1.906(4)
2.004(5)
1.957(5)
2.195(5)
2.141(6)
122.9(2)
92.62(19)
104.62(19)
116.2(3)
101.7(2)
102.2(2)
180.00
Zn(2)-O(7)
Zn(2)-O(9)
Zn(2)-O(3)#2
Zn(3)-O(9)
Zn(2)-N(5)
Zn(3)-O(9)#3
Zn(3)-O(8)
Zn(3)-O(8)#3
Zn(3)-O(4)#4
O(5)-Zn(1)-O(1)
O(1)-Zn(1)-N(3)#1
O(1)-Zn(1)-N(1)
O(9)-Zn(2)-O(3)#2
O(9)-Zn(2)-N(5)
O(9)-Zn(2)-O(7)
O(9) -Zn(3)-O(9)#3
O(8)-Zn(3)-O(8)#3
O(9)#3-Zn(3)-O(8)
O(9)-Zn(3)-O(4)#4
2
Zn(3)-O(4)#2
O(5)-Zn(1)-N(3)#1
O(5)-Zn(1)-N(1)
N(3)#1-Zn(1)-N(1)
O(3)#2-Zn(2)-O(7)
O(7)-Zn(2)-N(5)
O(3)#2-Zn(2)-N(5)
O(4)#2-Zn(3)-O(4)#4
O(9)-Zn(3)-O(8)
O(4)#4-Zn(3)-O(8)#3
O(8)-Zn(3)-O(4)#4
88.28(19)
98.5(2)
100.8(2)
Zn(1)-O(2)
1.916(2)
2.011(3)
2.005(2)
2.095(2)
2.021(3)
Zn(1)-N(5)#1
Zn(1)-N(3)#2
Zn(2)-O(4)#3
Zn(2)-O(2W)
Zn(2)-N(7)
1.987(3)
1.998(3)
2.298(2)
2.206(3)
2.283(3)
Zn(1)-O(1W)
Zn(2)-O(6)
Zn(2)-O(3)#3
Zn(2)-N(1)
22

Page 23 of 32
CrystEngComm
View Article Online
DOI: 10.1039/C4CE00835A
O(2)-Zn(1)-N(5)#1
N(5)#1-Zn(1)-N(3)#2
N(3)#2-Zn(1)-O(1W)
O(6)-Zn(2)-N(1)
O(6)-Zn(2)-O(3)#3
O(6)-Zn(2)-N(7)
O(2W)-Zn(2)-N(7)
O(3)#3-Zn(2)-O(4)#3
3
127.89(10)
O(2)-Zn(1)-N(3)#2
O(2)-Zn(1)-O(1W)
N(5)#1-Zn(1)-O(1W)
N(1)-Zn(2)-O(3)#3
N(1)-Zn(2)-O(2W)
O(3)#3-Zn(2)-N(7)
O(6)-Zn(2)-O(4)#3
O(2W)-Zn(2)-O(4)#3
98.39(10)
112.93(11)
109.14(10)
97.74(11)
109.84(10)
94.33(10)
172.31(9)
59.53(9)
105.54(11)
102.11(11)
152.06(10)
94.40(11)
89.12(10)
168.72(10)
89.69(9)
Zn(1)-O(5)
1.953(2)
Zn(1)-N(3)#1
2.005(2)
Zn(1)-O(1)
1.990(2)
Zn(1)-N(1)
2.029(2)
O(5)-Zn(1)-O(1)
O(1)-Zn(1)-N(3)#1
O(1)-Zn(1)-N(1)
4
110.30(11)
112.19(10)
103.43(10)
O(5)-Zn(1)-N(3)#1
O(5)-Zn(1)-N(1)
N(3)#1-Zn(1)-N(1)
117.15(10)
108.45(10)
104.14(9)
Zn(1)-O(1)
1.9398(16)
1.9427(16)
93.56(8)
Zn(1)-N(1)
1.9966(17)
2.0156(17)
118.84(8)
122.59(8)
100.30(8)
Zn(1)-O(4)#1
Zn(1)-N(3)#2
O(1)-Zn(1)-O(4)#1
O(4)#1-Zn(1)-N(1)
O(1)-Zn(1)-N(1)
O(1)-Zn(1)-N(3)#2
N(1)-Zn(1)-N(3)#2
119.41(8)
102.23(8)
O(4)#1-Zn(1)-N(3)#2
a
Symmetry transformations used to generate equivalent atoms: #1 x-1, y, z; #2 x+1, y, z+1;
#3 -x+2, -y, -z+2; #4 -x+1, -y, -z+1 for 1; #1 -x+1, -y+1, -z+1; #2 -x+1, -y, -z+1; #3 -x+2, -y,
-z for 2; #1 x, -y+3/2, z-1/2 for 3; #1 x-1/2, -y+1/2, z+1/2; #2 x-1, y, z for 4.
23

CrystEngComm
Page 24 of 32
View Article Online
DOI: 10.1039/C4CE00835A
Scheme and figure captions:
Scheme 1 Coordination modes of BDC-R appeared in complexes 1-4.
Fig. 1 (a) Coordination environment of Zn(II) in 1 with ellipsoids drawn at 30% probability
level. The hydrogen atoms and free water molecules are omitted for clarity. Symmetry code: A
x-1, y, z; B x+1, y, z+1; C -x+2, -y, -z+2; D -x+1, -y, -z+1; E -x+2, -y+3, -z+1; F -x+1, -y,
-z+2; G x+1, y, z. (b) 2D layer of 1 formed by Zn-BDC2- and tib. (c) 3D framework of 1. (d)
Topology of 1: turquoise, Zn1 atoms; bright green, Zn3(CO2)4(µ2-OH)2; purple, tib ligands. (e)
The schematic representation of 3-fold interpenetrating framework of 1.
Fig. 2 (a) Coordination environment of Zn(II) atoms in 2 with the ellipsoids drawn at the 30%
probability level. The hydrogen atoms are omitted for clarity. Symmetry code: A -x+1, -y+1,
-z+1; B -x+1, -y, -z+1; C -x+2, -y, -z. (b) 2D structure of 2. (c) Topology of 2: turquoise, Zn1
atoms; bright green, Zn2 building unit; purple, tib ligands.
Fig. 3 (a) Coordination environment of Zn(II) atoms in 3 with the ellipsoids drawn at the 30%
probability level. The hydrogen atoms are omitted for clarity. Symmetry code: A x, -y+3/2,
z-1/2; B -x+1, -y, -z+1. (b) 2D structure of 3. (c) The schematic representation of 3-fold
interpenetrating framework of 3.
Fig. 4 (a) Coordination environment of Zn(II) atoms in 4 with the ellipsoids drawn at the 30%
probability level. The hydrogen atoms and free water molecules are omitted for clarity.
Symmetry code: A x-1/2, -y+1/2, z+1/2; B x-1, y, z. (b) 2D structure of 4. (c) Topology of 4.
Fig. 5 H2O/MeOH/EtOH sorption isotherms at 298 K for 1′ (a)-4′ (e): filled shape, adsorption;
open shape, desorption.
Fig. 6 Emission spectra of 1-4 in the solid state at room temperature.
24

Page 25 of 32
CrystEngComm
View Article Online
DOI: 10.1039/C4CE00835A
a
b
c
d
e
f
g
Scheme 1
25

CrystEngComm
Page 26 of 32
View Article Online
DOI: 10.1039/C4CE00835A
(a)
(b)
(c)
(d)
(e)
Fig. 1
26

Page 27 of 32
CrystEngComm
View Article Online
DOI: 10.1039/C4CE00835A
(a)
(b)
(c)
Fig. 2
27

CrystEngComm
Page 28 of 32
View Article Online
DOI: 10.1039/C4CE00835A
(a)
(b)
(c)
Fig. 3
28

Page 29 of 32
CrystEngComm
View Article Online
DOI: 10.1039/C4CE00835A
(a)
(b)
(c)
Fig. 4
29