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 Page 1 of 32 CrystEngComm
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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

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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(µ 2-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
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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
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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
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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(µ 2-OH)2]·H2O (1),

[Zn2(tib)(BDC-NH2)SO4(H2O)2]·5H2O (2), [Zn2(tib)2(HBDC-OH)2(BDC-OH)]·2H2O (3) and

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[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

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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
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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).

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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),
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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

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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(µ 2-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
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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

µ 2-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 µ 2-O (O9, O9C)

shared with two different Zn2 atoms. Zn2 and Zn3 are bridged by one µ 2-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(µ 2-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)-µ2-BDC-NH2 coordination mode

(Scheme 1a), another one in (κ1)-(κ1-κ1)-µ3-BDC-NH2 mode (Scheme 1b), and the third one in

(κ1-κ1)-(κ1-κ1)-µ4-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 µ2- and µ4-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 µ3-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

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multidimensional structure to simple node-and-linker net was carried out. The above

mentioned Zn3(OCO)4(µ 2-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

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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

(O3C, O4C) from one BDC-NH2 ligand and two oxygen ones (O6, O2W) from one SO42-

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 µ3-bridging mode to connect three Zn(II) atoms with its carboxylate groups in

(κ1)-(κ2)-µ2-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-,

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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)

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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 µ2-bridging and terminal ligands, respectively, the

BDC-OH with its carboxylate groups in (κ1)-(κ1)-µ2-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,

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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 µ2-bridging mode with its carboxylate groups in

(κ1)-(κ1)-µ2-BDC-NH2 coordination mode (Scheme 1g) and connects the 1D chains to give a
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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 µ 2-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

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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
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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

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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
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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

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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
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CrystEngComm Accepted Manuscript

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

M-MIL-53 (M = Al or Cr)29a,29b or Al-MIL-53-NH229c and can be interpreted into the

12
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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
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CrystEngComm Accepted Manuscript

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

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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
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CrystEngComm Accepted Manuscript

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).

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Table 1 Crystal Data and Structure Refinements for Complexes 1-4.

1 2 3 4

Empirical formula C62H48N16O19Zn5 C23H31N7O15SZn2 C54H42N12O17Zn2 C23H17N7O7Zn

Formula weight 1648.01 808.35 1261.74 568.81

Crystal system Triclinic Triclinic Monoclinic Monoclinic

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Space group P-1 P-1 P21/c P21/n

a /Å 11.539(3) 7.999(10) 14.6517(16) 10.426(5)

b /Å 11.562(3) 11.703(5) 7.8277(8) 18.990(10)

c /Å 14.283(3) 17.386(2) 22.551(2) 11.711(6)

α /° 99.419(3) 104.387(2) 90 90

β /° 96.191(3) 98.557(2) 90.01(2) 96.875(10)

γ /° 117.938(3) 96.306(2) 90 90

V /Å3 1623.2(6) 1540.5(3) 2586.4(5) 2302.0(2)

Z 1 2 2 4

Dc /g cm-3 1.686 1.743 1.620 1.641

µ /mm-1 1.908 1.709 1.017 1.129

F(000) 834 828 1292 1160

Reflections 11637 8655 18763 13137

collected

Unique reflections 5614 5409 5082 4285

Goodness-of-fit 1.019 1.034 1.075 1.039

R1a [I > 2σ (I)] 0.0663 0.0368 0.0393 0.0297

wR2b [I > 2σ (I)] 0.1852 0.0975 0.1150 0.0829

a
R1 =Σ||Fo| - |Fc||/Σ|Fo|. b
wR2 = |Σw(|Fo|2 - |Fc|2)|/Σ|w(Fo)2|1/2, where w = 1/[σ2(Fo2) + (aP)2 +

bP]. P = (Fo2 + 2Fc2)/3.

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Table 2 Selected Bond Lengths (Å) and Angles (deg) for Complexes 1-4 a.

Zn(1)-O(5) 1.934(4) Zn(1)-N(1) 2.033(5)

Zn(1)-O(1) 1.962(5) Zn(1)-N(3)#1 2.001(5)

Zn(2)-O(7) 1.943(4) Zn(2)-O(9) 1.906(4)

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Zn(2)-O(3)#2 1.927(6) Zn(2)-N(5) 2.004(5)

Zn(3)-O(9) 1.918(4) Zn(3)-O(9)#3 1.957(5)

Zn(3)-O(8) 2.207(5) Zn(3)-O(8)#3 2.195(5)

Zn(3)-O(4)#4 2.141(6) Zn(3)-O(4)#2 2.141(6)

O(5)-Zn(1)-O(1) 106.6(2) O(5)-Zn(1)-N(3)#1 122.9(2)

O(1)-Zn(1)-N(3)#1 104.9(2) O(5)-Zn(1)-N(1) 92.62(19)

O(1)-Zn(1)-N(1) 127.1(2) N(3)#1-Zn(1)-N(1) 104.62(19)

O(9)-Zn(2)-O(3)#2 112.4(2) O(3)#2-Zn(2)-O(7) 116.2(3)

O(9)-Zn(2)-N(5) 120.2(2) O(7)-Zn(2)-N(5) 101.7(2)

O(9)-Zn(2)-O(7) 104.23(19) O(3)#2-Zn(2)-N(5) 102.2(2)

O(9) -Zn(3)-O(9)#3 157.96(8) O(4)#2-Zn(3)-O(4)#4 180.00

O(8)-Zn(3)-O(8)#3 160.61(7) O(9)-Zn(3)-O(8) 88.28(19)

O(9)#3-Zn(3)-O(8) 87.68(19) O(4)#4-Zn(3)-O(8)#3 98.5(2)

O(9)-Zn(3)-O(4)#4 103.1(2) O(8)-Zn(3)-O(4)#4 100.8(2)

Zn(1)-O(2) 1.916(2) Zn(1)-N(5)#1 1.987(3)

Zn(1)-O(1W) 2.011(3) Zn(1)-N(3)#2 1.998(3)

Zn(2)-O(6) 2.005(2) Zn(2)-O(4)#3 2.298(2)

Zn(2)-O(3)#3 2.095(2) Zn(2)-O(2W) 2.206(3)

Zn(2)-N(1) 2.021(3) Zn(2)-N(7) 2.283(3)

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O(2)-Zn(1)-N(5)#1 127.89(10) O(2)-Zn(1)-N(3)#2 98.39(10)

N(5)#1-Zn(1)-N(3)#2 112.93(11) O(2)-Zn(1)-O(1W) 105.54(11)

N(3)#2-Zn(1)-O(1W) 109.14(10) N(5)#1-Zn(1)-O(1W) 102.11(11)

O(6)-Zn(2)-N(1) 97.74(11) N(1)-Zn(2)-O(3)#3 152.06(10)

O(6)-Zn(2)-O(3)#3 109.84(10) N(1)-Zn(2)-O(2W) 94.40(11)

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O(6)-Zn(2)-N(7) 94.33(10) O(3)#3-Zn(2)-N(7) 89.12(10)

O(2W)-Zn(2)-N(7) 172.31(9) O(6)-Zn(2)-O(4)#3 168.72(10)

O(3)#3-Zn(2)-O(4)#3 59.53(9) O(2W)-Zn(2)-O(4)#3 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) 110.30(11) O(5)-Zn(1)-N(3)#1 117.15(10)

O(1)-Zn(1)-N(3)#1 112.19(10) O(5)-Zn(1)-N(1) 108.45(10)

O(1)-Zn(1)-N(1) 103.43(10) N(3)#1-Zn(1)-N(1) 104.14(9)

Zn(1)-O(1) 1.9398(16) Zn(1)-N(1) 1.9966(17)

Zn(1)-O(4)#1 1.9427(16) Zn(1)-N(3)#2 2.0156(17)

O(1)-Zn(1)-O(4)#1 93.56(8) O(1)-Zn(1)-N(1) 118.84(8)

O(4)#1-Zn(1)-N(1) 119.41(8) O(1)-Zn(1)-N(3)#2 122.59(8)

O(4)#1-Zn(1)-N(3)#2 102.23(8) N(1)-Zn(1)-N(3)#2 100.30(8)

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.

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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,
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-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(µ 2-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.

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Scheme 1
e
a
b

25
f
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g
d
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Fig. 1
(b)

(d)

26
(a)
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(c)

(e)
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Fig. 2

27
(b)
(a)

(c)
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Fig. 3

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(c)
(a)

(b)
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Fig. 4

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(c)
(a)

(b)
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1.6 H2O at 298 K 7 H2O at 298 K

1.4
6
1.2
5
1.0 MeOH at 298 K
na/mol mol-1

na/mol mol-1
4 MeOH at 298 K
0.8
3
0.6
EtOH at 298 K
0.4 2 EtOH at 298 K
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0.2 1

0.0 0

0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
p / atm p / atm

(a) (b)

3.5
4
3.0 MeOH at 298 K

H2O at 298 K 2.5

3
H2O at 298 K
2.0
na/mol mol-1

na/mol mol-1

2
1.5
EtOH at 298 K
MeOH at 298 K 1.0
1
EtOH at 298 K 0.5

0 0.0

0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
p / atm P / atm

(c) (d)

Fig. 5

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Fig. 6
350
400
450

31
Wavelength/nm
500
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4
3
2
1

600
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Graphical content entry:

Four new zinc(II) complexes were synthesized by varying the substituent groups of

1,4-benzenedicarboxylate, and their luminescence and sorption properties were studied.

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