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Assembly of a series of zinc coordination

polymers based on 1,4-bis[2-(4-pyridyl)ethenyl]-
Cite this: CrystEngComm, 2014, 16,
2,3,5,6-tetramethylbenzene and
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6621

1,3-benzenedicarboxylate derivatives†
Yu Ge,a Ni-Ya Li,a Xue-Ying Ji,a Jun-Feng Wang,a Dong Liu*a and Xiao-Yan Tang*b

Five new coordination polymers, namely, [Zn(1,3-BDC)(1,4-bpetmb)]n (1), {[Zn2(5-Cl-1,3-BDC)2(1,4-bpetmb)2]·MeCN}n

(2), [Zn(5-NO2-1,3-BDC)(1,4-bpetmb)0.5]n (3), {[Zn(5-NH2-1,3-BDC)(1,4-bpetmb)0.5]·2H2O}n (4) and
[Zn2(μ-OH)(1,3,5-BTC)(1,4-bpetmb)]n (5) have been synthesized under solvothermal conditions, based on
the bis-pyridyl linker 1,4-bis[2-(4-pyridyl)ethenyl]-2,3,5,6-tetramethylbenzene (1,4-bpetmb) along with
1,3-benzenedicarboxylate (1,3-BDC) or its derivatives such as 5-chloro-1,3-benzenedicarboxylate (5-Cl-1,3-BDC),
5-nitro-1,3-benzenedicarboxylate (5-NO2-1,3-BDC), 5-amino-1,3-benzenedicarboxylate (5-NH2-1,3-BDC)
and 1,3,5-benzenetricarboxylate (1,3,5-BTC). Compounds 1–5 have been characterized by elemental
analysis, IR spectroscopy, powder X-ray diffraction (PXRD) and unambiguously by single crystal X-ray
Received 3rd April 2014, diffraction analysis. 1 and 2 feature the 2D (4,4) net. 3 comprises an interlocked 3D framework, and the
Accepted 19th May 2014
3D framework is derived from the inclined interpenetration of the 2D (4,4) net. 4 exhibits a thick 2D
(3,4)-connected network with a Schläfli symbol of (63)(65·8). 5 displays a 3D two-fold interpenetrating
DOI: 10.1039/c4ce00696h
(3,5)-connected framework with the Schläfli symbol of (63)(67·83). Thermal stability and solid-state
www.rsc.org/crystengcomm photoluminescence properties of 1–5 were also investigated.

Introduction the structures and properties of these complexes are usually

influenced by the flexibility, shape, symmetry, length and
There has been an enormous growth in coordination poly- substituent groups of ligands.4
mers during the last two decades not only due to their Recently, we have been interested in the construction of
intriguing architectures but also for their potential applica- coordination polymers based on the mixed multicarboxylates
tions as functional materials in the areas of photolumi- and multipyridyl ligands.9 Multicarboxylates are often used
nescence, catalysis, adsorption, separation and magnetism.1–10 as bridging ligands to produce coordination polymers due to
Although a number of interesting coordination polymers with their versatile coordination modes, high structural stability
interesting topologies based on the assembly of metal centers and the ability to balance the positive charges.10 On the other
and organic ligands using the principles of crystal engineering hand, the multipyridyl ligands can be employed as ancillary
have been reported, a rational synthesis strategy to control the ligands, together with the carboxylate ligands, to meet and
assembly of building blocks to generate desired coordination satisfy the requirements for coordination geometries of metal
polymers is still one of the great challenges in this area.1–10 ions in the assembly process.11 By combining these O-donor
Many factors affected the structural assembly process of and N-donor ligands with transition metal ions, for example,
these complexes, such as the metal salts, organic ligands, ZnII, which possess d10 configurations, the resulting coordination
temperatures, pH values, solvents and so on.3–8 Among them, polymers can exhibit appealing structures as well as photo-
the ligands play very important roles to tune the structural luminescence properties.12 In our previous work, we employed a
architectures and functionalities of coordination polymers as long dipyridyl ligand 1,4-bis[2-(4-pyridyl)ethenyl]benzene (1,4-bpeb)
as one component to construct coordination polymers.9b–e
a
College of Chemistry and Materials Science, Huaibei Normal University, Very recently, such a ligand has also been well investigated in
Huaibei 235000, PR China. E-mail: [email protected]; Fax: +86 561 3806281 some particularly elegant work by Vittal and co-workers.10e,f
b
School of Chemistry and Materials Engineering, Changshu Institute of Technology,
In view of these reported results, we found that the structure
Changshu 215500, Jiangsu, PR China. E-mail: [email protected]
† Electronic supplementary information (ESI) available: Experimental section
of a coordination polymer can be greatly affected by the
and figures. CCDC 977633–977637. For ESI and crystallographic data in CIF or choice of carboxylate. The different functional groups in the
other electronic format see DOI: 10.1039/c4ce00696h 5-position of 1,3-benzenedicarboxylate (1,3-BDC) could even

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form distinct networks.9d In addition, a 1,3-BDC derivative (0.35 g, 10 mol%) and triethylamine (3.03 g, 30 mmol) in
may also react with other N-donor ligands and afford coor- 20 mL of DMF solution. The mixture was heated at 110 °C
dination polymers with different structures.8h,i Since the for a period of 30 h and then diluted with Et2O (60 mL) to
1,4-bpeb ligand may also be modified, a question flashed precipitate the product. The 1,4-bpetmb ligand was washed
into our mind. If we prepare a new ligand of 1,4-bpeb deriva- with Et2O (4 × 10 mL) and collected as a light yellow powder.
tive, can the newly formed ligand react with carboxylates Yield: 2.45 g (72%). Anal. calcd for C24H24N2: C 84.67; H 7.11;
and metal ions to generate interesting coordination networks N 8.23. Found: C 84.41; H 6.89; N 7.96. IR (KBr, cm−1):
which are different with those constructed by 1,4-bpeb and 3422m, 3018w, 1636m, 1593s, 1548m, 1495m, 1414s, 1383m,
similar metal ions and carboxylate ligands? In order to achieve 1215m, 1068w, 973s, 878m, 835s, 787s, 616m, 558s, 530s,
this goal, we synthesized a new dipyridyl ligand 1,4-bis[2-(4- 444m. 1H NMR (400 MHz, d6-DMSO, 298 K, TMS): δ = 8.56
pyridyl)ethenyl]-2,3,5,6-tetramethylbenzene (1,4-bpetmb). The (d, J = 5.2 Hz, 4H, Py–H), 7.63 (d, J = 16.8 Hz, 2H, CHCH),
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difference between the 1,4-bpetmb and 1,4-bpeb ligand is that 7.58 (d, J = 4.8 Hz, 4H, Py–H), 6.46 (d, J = 16.8 Hz, 2H,
the four phenyl hydrogen atoms in 1,4-bpeb are replaced by CHCH), 2.21 (s, 12H, Me–H) (Fig. S1, ESI†).
four methyl groups in 1,4-bpetmb. In this work, 1,3-BDC and Preparation of [Zn(1,3-BDC)(1,4-bpetmb)]n (1). To a 10 mL
four types of its derivatives, 5-chloro-1,3-benzenedicarboxylate Pyrex glass tube was loaded Zn(NO3)2·6H2O (30 mg, 0.1 mmol),
(5-Cl-1,3-BDC), 5-nitro-1,3-benzenedicarboxylate (5-NO2-1,3-BDC), 1,4-bpetmb (34 mg, 0.1 mmol), 1,3-H2BDC (17 mg, 0.1 mmol),
5-amino-1,3-benzenedicarboxylate (5-NH2-1,3-BDC) and 1,3,5- 2 mL of H2O and 1 mL of MeCN. The glass tube was sealed
benzenetricarboxylate (1,3,5-BTC), were selected as O-donor and heated in an oven to 170 °C for 3 days, and then cooled to
ligands to react with 1,4-bpetmb and ZnII ions under solvo- ambient temperature at the rate of 5 °C h−1. Yellow block
thermal conditions, and five 2D or 3D coordination polymers crystals were collected and washed with H2O/MeCN (2 : 1 v/v).
have been afforded. They are formulated as [Zn(1,3-BDC)(1,4- Yield: 46 mg (81% yield based on Zn). Anal. calcd for
bpetmb)]n (1), {[Zn2(5-Cl-1,3-BDC)2(1,4-bpetmb)2]·MeCN}n (2), C32H28N2O4Zn: C 67.43; H 4.95; N 4.91. Found: C 67.87;
[Zn(5-NO2-1,3-BDC)(1,4-bpetmb)0.5]n (3), {[Zn(5-NH2-1,3-BDC)(1,4- H 4.72; N 5.26. IR (KBr, cm−1): 3419m, 2916w, 1616s, 1575m,
bpetmb)0.5]·2H2O}n (4) and [Zn2(μ-OH)(1,3,5-BTC)(1,4-bpetmb)]n 1504m, 1426s, 1378s, 1221m, 1200m, 1117w, 1069m, 1015s,
(5), where abundant structural diversity has been observed 979m, 855m, 838s, 798m, 727s, 681m, 617m, 574m, 533s,
because of the influence of substituent groups in 1,3-BDC. 443m.
Furthermore, these structures are also different from those Preparation of {[Zn2(5-Cl-1,3-BDC)2(1,4-bpetmb)2]·MeCN}n
constructed by ZnII ions, 1,4-bpeb and corresponding 1,3-BDC (2). Compound 2 (yellow blocks) was prepared as above
derivatives.9c,d The structural differences may be caused by starting from Zn(NO3)2·6H2O (30 mg, 0.1 mmol), 1,4-bpetmb
the steric hindrance of four methyl groups in the 1,4-bpetmb (34 mg, 0.1 mmol), 5-Cl-1,3-H2BDC (20 mg, 0.1 mmol), 2 mL
ligand. Herein, we report the syntheses, crystal structures, of H2O and 1 mL of MeCN. Yield: 53 mg (85% yield based
thermal and photoluminescence properties of 1–5. on Zn). Anal. calcd for C66H57Cl2N5O8Zn2: C 63.42; H 4.60;
N 5.60. Found: C 63.76; H 4.23; N 5.69. IR (KBr, cm−1):
Experimental 3471m, 2917w, 1616s, 1576m, 1505m, 1405s, 1220m, 1166m,
Materials and physical measurements 1069m, 1015m, 973m, 883m, 836s, 793m, 746s, 693m, 661m,
618m, 577m, 532s, 445m.
All chemicals and reagents were obtained from commercial Preparation of [Zn(5-NO2-1,3-BDC)(1,4-bpetmb)0.5]n (3).
sources and used without further purification. Infrared (IR) Compound 3 (yellow blocks) was prepared as above starting
samples were prepared as KBr pellets, and the spectrum was from Zn(NO3)2·6H2O (30 mg, 0.1 mmol), 1,4-bpetmb (34 mg,
obtained in the 4000–400 cm−1 range using a Nicolet Avatar 0.1 mmol), 5-NO2-1,3-H2BDC (21 mg, 0.1 mmol), 2 mL of H2O
360 FT-IR spectrophotometer. The elemental analyses for C, and 1 mL of MeCN. Yield: 34 mg (76% yield based on Zn).
H and N were performed using an EA1110 CHNS elemental Anal. calcd. for C20H15N2O6Zn: C, 54.01; H, 3.40; N, 6.30.
analyzer. 1H NMR spectra were recorded at ambient tempera- Found: C, 53.82; H, 3.18; N, 6.61. IR (KBr, cm−1): 3419m,
ture using a Bruker Avance-III 400 MHz NMR spectrometer. 2916m, 1616s, 1573m, 1504m, 1426m, 1378s, 1222m, 1200m,
1
H NMR chemical shifts were referenced to the solvent signal 1117w, 1069m, 1015m, 979m, 885m, 838s, 772m, 731s, 681m,
in d6-DMSO. Powder XRD patterns were obtained using a 615m, 574m, 534s, 443m.
PANalytical X'Pert PRO MPD system (PW3040/60). Thermal Preparation of {[Zn(5-NH2-1,3-BDC)(1,4-bpetmb)0.5]·2H2O}n (4).
analysis was performed with a Perkin-Elmer TGA-7 thermo- Compound 4 (yellow blocks) was prepared as above
gravimetric analyser at a heating rate of 10 °C min−1 and a starting from Zn(NO3)2·6H2O (30 mg, 0.1 mmol), 1,4-bpetmb
flow rate of 100 cm3 min−1 (N2). The photoluminescence spec- (34 mg, 0.1 mmol), 5-NH2-1,3-H2BDC (18 mg, 0.1 mmol), 2 mL
tra were obtained using a JASCO FP-8600 spectrofluorometer. of H2O and 1 mL of MeCN. Yield: 36 mg (80% yield based on
Zn). Anal. calcd. for C20H21N2O6Zn: C, 53.29; H, 4.70; N, 6.21.
Preparation of 1,4-bpetmb and complexes 1–5 Found: C, 52.97; H, 4.91; N, 6.13. IR (KBr, cm−1): 3428s,
Preparation of 1,4-bpetmb. A 100 mL round-bottom flask 3060m, 1655s, 1648s, 1541m, 1508m, 1478m, 1352s, 1206m,
was charged with 1,4-diiodo-2,3,5,6-tetramethylbenzene (3.86 g, 1132w, 1070m, 1029m, 965m, 934m, 870m, 837s, 823m,
10 mmol), 4-vinylpyridine (3.16 g, 30 mmol), PdCl2(PPh3)2 797m, 731s, 679m, 618m, 572m, 536s, 450m.

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Preparation of [Zn2(μ-OH)(1,3,5-BTC)(1,4-bpetmb)]n (5). at 170 °C for 3 days gave rise to yellow blocks of 1. Analogous
Compound 5 (yellow diamondoid crystals) was prepared as reaction using 5-Cl-1,3-H2BDC to replace 1,3-H2BDC afforded
above starting from Zn(NO3)2·6H2O (30 mg, 0.1 mmol), crystals of 2. Although the topological structure of 2 is similar
1,4-bpetmb (34 mg, 0.1 mmol), 1,3,5-H3BTC (21 mg, 0.1 mmol), to that of 1, there are some differences between their struc-
2 mL of H2O and 1 mL of MeCN. Yield: 25 mg (72% yield based tures. Compared with that of 1, the unit cell volume of 2 is a
on Zn). Anal. calcd. for C33H28N2O7Zn2: C, 57.00; H, 4.06; bit stretched and formed small cavities to hold solvent MeCN
N, 4.03. Found: C, 56.71; H, 3.94; N, 4.15. IR (KBr, cm −1): molecules. This phenomenon may be caused by the steric
3429m, 3026m, 1616s, 1560s, 1506m, 1439m, 1382s, 1222m, hindrance of the chloride atom in the 5-position of 1,3-BDC.
1100m, 1070w, 1024m, 973m, 839s, 793m, 744m, 718s, 617m, The obtained results impelled us to investigate whether more
574m, 530s, 445m. coordination polymers with diverse structural motifs can be
obtained when other 1,3-H2BDC derivates were used. Hence,
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X-Ray data collection and structure determination 5-NO2-1,3-H2BDC, 5-NH2-1,3-H2BDC and 1,3,5-H3BTC were
Single-crystal X-ray diffraction data for 1–5 were collected chosen as the carboxylate ligands to react with Zn(NO3)2·6H2O
using a Bruker SMART APEX II CCD diffractometer equipped and 1,4-bpetmb and afforded the crystals of 3, 4 and 5,
with graphite-monochromated Mo-Kα (λ = 0.71073 Å) by respectively.
using the Φ/ω scan technique. Absorption correction was Compounds 1–5 are air- and moisture-stable. The elemental
based on symmetry equivalent reflections using the SADABS analysis was consistent with their chemical formulas. The IR
program.13 The crystal structure of 1–5 were solved by direct spectra of 1–5 show strong peaks in the range of 1620–1510 cm−1
methods and refined on F 2 by full-matrix least-squares and 1450–1350 cm−1, indicating that they all contain coordi-
methods with the SHELXL-97 program.14 All non-hydrogen nated carboxylic groups.15 The strong peaks in the range of
atoms were refined anisotropically. The H atoms of the sol- 840–835 cm−1 and middle peaks in the range of 610–620 cm−1
vent water molecule in 4 and the hydroxy group in 5 were and 440–455 cm−1 indicate the existence of pyridyl groups in
located from the Fourier map and included in the final refine- five complexes.15 The identities of 1–5 were further confirmed
ment by use of geometrical restraints with the O–H distances by single crystal X-ray diffraction analysis. Powder X-ray dif-
fixed at 0.85 Å and Uiso(H) equivalent to 1.5 times of Ueq(O). fraction (PXRD) analyses of 1–5 were carried out at room tem-
All other H atoms were introduced at the calculated positions perature. For 1–5, the measured PXRD patterns are in good
and included in the structure-factor calculations. A summary agreement with the simulated patterns generated from the
of key crystallographic information for 1–5 is given in Table 1. results of single crystal X-ray diffraction data, which reveal the
Selected bond lengths and angles for 1–5 are listed in Table 2. phase purity of the bulk crystalline materials (Fig. S2, ESI†).

Results and discussion Crystal structures of 1–3

Synthetic and spectral aspects Compounds 1 and 2 crystallize in the triclinic space group P1̄. For
Solvothermal reaction among Zn(NO3)2·6H2O, 1,4-bpetmb 1, the asymmetric unit contains one [Zn(1,3-BDC)(1,4-bpetmb)]
and 1,3-H2BDC in a 1 : 1 : 1 molar ratio in H2O/MeCN (2 : 1 v/v) unit. The Zn1 atom is coordinated by two N atoms from two

Table 1 Summary of crystallographic data for 1–5

Compounds 1 2 3 4 5
Chemical formula C32H28N2O4Zn C66H57Cl2N5O8Zn2 C20H15N2O6Zn C20H21N2O6Zn C33H28N2O7Zn2
Formula weight 569.95 1249.85 444.73 450.78 695.35
Crystal system Triclinic Triclinic Monoclinic Monoclinic Monoclinic
a/Å 9.4258(19) 9.907(2) 10.791(2) 16.096(3) 18.621(4)
b/Å 10.052(2) 10.421(2) 17.717(3) 7.6958(15) 9.7191(19)
c/Å 15.309(3) 16.142(3) 9.7094(19) 16.148(3) 17.267(4)
α/° 97.47(3) 81.18(3) 90.00 90.00 90.00
β/° 105.32(3) 75.18(3) 92.49(3) 99.06(3) 98.76(3)
γ/° 103.94(3) 81.78(3) 90.00 90.00 90.00
V/Å3 1328.4(6) 1582.6(6) 1854.5(6) 1975.3(7) 3088.5(12)
Temperature/K 223(2) 223(2) 223(2) 223(2) 223(2)
Space group P1̄ P1̄ P21/c P21/c P21/c
Z 2 1 4 4 4
Total reflections 11 832 11 088 8181 8602 14 288
Unique reflections 4688 5580 3281 3497 5434
Rint 0.0232 0.0406 0.0434 0.0461 0.0520
R1 (I > 2σ(I)) 0.0395 0.0513 0.0570 0.0791 0.0792
wR(F 2) (I > 2σ(I)) 0.1114 0.1301 0.1657 0.2270 0.2100
R1 (all data) 0.0438 0.0670 0.0646 0.0915 0.1085
wR(F 2) (all data) 0.1154 0.1410 0.1741 0.2498 0.2447
Goodness of fit on F 2 1.069 1.037 1.077 1.038 0.991

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Table 2 Selected bond lengths (Å) and angles (deg) for 1–5a

Complex 1
Zn(1)–O(4A) 2.0059(19) Zn(1)–O(3B) 2.070(2)
Zn(1)–O(1) 2.1197(18) Zn(1)–N(1) 2.166(2)
Zn(1)–N(2C) 2.184(2) Zn(1)–O(2) 2.324(2)
O(4A)–Zn(1)–O(3B) 114.16(8) O(4A)–Zn(1)–O(1) 150.12(8)
O(3B)–Zn(1)–O(1) 95.52(8) O(4A)–Zn(1)–N(1) 92.82(9)
O(3B)–Zn(1)–N(1) 84.27(9) O(1)–Zn(1)–N(1) 86.57(8)
O(4A)–Zn(1)–N(2C) 96.14(9) O(3B)–Zn(1)–N(2C) 87.44(9)
O(1)–Zn(1)–N(2C) 88.16(8) N(1)–Zn(1)–N(2C) 169.70(9)
O(4A)–Zn(1)–O(2) 91.01(8) O(3B)–Zn(1)–O(2) 153.75(7)
O(1)–Zn(1)–O(2) 59.11(7) N(1)–Zn(1)–O(2) 87.33(8)
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N(2C)–Zn(1)–O(2) 97.54(8)

Complex 2
Zn(1)–O(2A) 2.049(2) Zn(1)–O(1) 2.050(2)
Zn(1)–O(4B) 2.065(2) Zn(1)–N(2C) 2.146(3)
Zn(1)–N(1) 2.148(3) Zn(1)–O(3B) 2.426(3)
O(2A)–Zn(1)–O(1) 124.85(10) O(2A)–Zn(1)–O(4B) 93.00(11)
O(1)–Zn(1)–O(4B) 142.15(10) O(2A)–Zn(1)–N(2C) 90.28(11)
O(1)–Zn(1)–N(2C) 88.70(10) O(4B)–Zn(1)–N(2C) 91.28(11)
O(2A)–Zn(1)–N(1) 90.11(11) O(1)–Zn(1)–N(1) 86.89(10)
O(4B)–Zn(1)–N(1) 93.79(11) N(2)–Zn(1)–N(1) 174.89(10)
O(2A)–Zn(1)–O(3B) 150.14(10) O(1)–Zn(1)–O(3B) 84.81(9)
O(4B)–Zn(1)–O(3B) 57.44(10) N(2C)–Zn(1)–O(3B) 94.19(11)
N(1)–Zn(1)–O(3B) 88.00(10)

Complex 3
Zn(1)–O(3A) 1.950(3) Zn(1)–O(1) 1.966(3)
Zn(1)–O(2B) 2.006(3) Zn(1)–N(1) 2.024(3)
O(3A)–Zn(1)–O(1) 126.99(13) O(3A)–Zn(1)–O(2B) 92.31(12)
O(1)–Zn(1)–O(2B) 108.69(12) O(3A)–Zn(1)–N(1) 117.86(14)
O(1)–Zn(1)–N(1) 102.34(13) O(2B)–Zn(1)–N(1) 106.40(14)

Complex 4
Zn(1)–O(1) 1.944(3) Zn(1)–O(4A) 1.983(3)
Zn(1)–N(1) 2.037(4) Zn(1)–N(2B) 2.094(4)
O(1)–Zn(1)–O(4A) 103.82(14) O(1)–Zn(1)–N(1) 103.06(16)
O(4A)–Zn(1)–N(1) 131.59(16) O(1)–Zn(1)–N(2B) 109.86(15)
O(4A)–Zn(1)–N(2B) 103.15(15) N(1)–Zn(1)–N(2B) 104.47(16)

Complex 5 Fig. 1 (a) View of the coordination environment of Zn1 in 1 with

Zn(1)–O(7) 1.910(5) Zn(1)–O(5A) 1.965(5) labeling scheme. (b) View of the 1D [Zn(1,3-BDC)]n chain in 1. (c) View
Zn(1)–N(1) 2.003(5) Zn(1)–O(1) 2.011(4) of the 2D [Zn(1,3-BDC)(1,4-bpetmb)]n network of 1. All hydrogen
Zn(2)–O(7) 1.884(4) Zn(2)–O(4B) 1.949(5) atoms are omitted for clarity. The cyan, red and blue balls represent
Zn(2)–O(2) 1.975(4) Zn(2)–N(2C) 2.049(6) zinc, oxygen and nitrogen atoms, respectively. Symmetry codes: (A) x − 1, y,
O(7)–Zn(1)–O(5A) 105.9(2) O(7)–Zn(1)–N(1) 111.6(2) z + 1; (B) x, y + 1, z; (C) −x + 1, −y + 1, −z + 1.
O(5A)–Zn(1)–N(1) 128.7(2) O(7)–Zn(1)–O(1) 102.84(19)
O(5A)–Zn(1)–O(1) 101.93(18) N(1)–Zn(1)–O(1) 102.36(19)
O(7)–Zn(2)–O(4B) 110.1(2) O(7)–Zn(2)–O(2) 106.7(2)
O(4B)–Zn(2)–O(2) 114.8(2) O(7)–Zn(2)–N(2C) 107.3(2) are linked by 1,4-bpetmb to give rise to a 2D (4,4) network of
O(4B)–Zn(2)–N(2C) 115.3(2) O(2)–Zn(2)–N(2C) 101.9(2) [Zn(1,3-BDC)(1,4-bpetmb)]n extending in the bc plane (Fig. 1c).
Owing to the influence of methyl groups in 1,4-bpetmb ligands,
a
Symmetry codes for 1: (A) x, y + 1, z; (B) −x + 1, −y + 1, −z + 1; (C) x
− 1, y, z + 1; for 2: (A) −x + 1, −y + 2, −z + 1; (B) x − 1, y, z; (C) x − 1, y the structure of 1 is obviously different from the 3D (4,6)-connected
+ 1, z + 1; for 3: (A) x, y, z − 1; (B) −x + 1, −y + 1, −z; for 4: (A) x, −y + framework of {[Zn6(μ-OH2)(1,3-BDC)6(1,4-bpeb)4]·MeCN}n and
1/2, z − 1/2; (B) x, −y + 3/2, z − 1/2; for 5: (A) x, −y + 1/2, z − 1/2; (B) x, the pcu network of {[Zn8(1,3-BDC)8(1,4-bpeb)4]·2H2O}n.9c
−y + 3/2, z − 1/2; (C) x + 1, y − 1, z.
The asymmetric unit of 2 contains one [Zn(5-Cl-1,3-BDC)(1,4-
bpetmb)] unit and one half of the solvent MeCN molecule. As
shown in Fig. S3a,† each Zn atom is located in an octahedral
different 1,4-bpetmb ligands and four O atoms from three coordination environment, coordinated by two N atoms from
1,3-BDC ligands to complete the octahedral geometry two different 1,4-bpetmb ligands and four O atoms from
(Fig. 1a). In 1, each adjoining pair of Zn atoms is connected three 5-Cl-1,3-BDC ligands. Similar to that found in 1, each
by 1,3-BDC ligands to form a [Zn(1,3-BDC)]n chain extending pair of Zn atoms is linked by 5-Cl-1,3-BDC ligands to form a
along the b axis (Fig. 1b). The adjacent [Zn(1,3-BDC)]n chains [Zn(5-Cl-1,3-BDC)]n chain extending along the a axis (Fig. S3b†).

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The neighbouring [Zn(5-Cl-1,3-BDC)]n chains are further

bridged by 1,4-bpetmb to generate a 2D [Zn(5-Cl-1,3-BDC)(1,4-
bpetmb)]n network extending in the ac plane (Fig. 2). It is
noted that when the carboxylate ligand 1,3-BDC was replaced
by 5-Cl-1,3-BDC, the topological net of 2 is similar to that
of 1. However, there are still minor differences between the
structures of 1 and 2. Compared with the structure of 1, the
obvious feature of 2 is the solvent MeCN molecules were
found in 2 (Fig. 2). In addition, the expanding directions of
the 2D network of 2 are also different from those of 1.
Different from 1 and 2, compound 3 crystallizes in the
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monoclinic space group P21/c, and the asymmetric unit con-

sists of one half of the [Zn2(5-NO2-1,3-BDC)2(1,4-bpetmb)]
unit. Compared with 1 and 2, the basic feature of 3 is the
coordination mode of Zn atoms in 3. Each Zn1 atom in 3 is
four-coordinated with a distorted tetrahedral environment.
Three sites are occupied by the O atoms from three different
5-NO2-1,3-BDC ligands, while the remaining one is filled with
the N atom from the 1,4-bpetmb molecule (Fig. 3a). Such a
coordination mode of the Zn center is obviously different
from those found in 1 and 2. Zn1 and its symmetry-related
Zn1A are bridged by two 5-NO2-1,3-BDC ligands to generate a
dinuclear [Zn2(5-NO2-1,3-BDC)2] unit. Each [Zn2(5-NO2-1,3-BDC)2]
unit is interlinked via the 5-NO2-1,3-BDC bridges to its equivalent
ones to form a [Zn(5-NO2-1,3-BDC)]n chain extending along
the c axis (Fig. 3b). Such a chain connects its adjacent ones
via 1,4-bpetmb bridges to form a 2D (4,4) layer with rectangular
grids (9.709 × 19.931 Å2) extending in the bc plane (Fig. 3c).
Owing to the existence of large sized grids, each of these 2D
layers has an infinite number of other equivalent ones passing
through it and finally afforded an infrequent interlocked 2D →
3D network through inclined interpenetration (Fig. 3d). As
shown in Fig. 3e, each grid in a 2D layer is interlocked by other
two 2D layers. Previously, 5-NO2-1,3-BDC was also used
as the dicarboxylate ligand to react with ZnII and 1,4-bpeb by
us. In that time, a 3D (3,4)-connected supramolecular framework
of {[Zn(5-NO2-1,3-BDC)(1,4-bpeb)]·2(H2O)0.5}n was formed.9d

Fig. 3 (a) View of the coordination environment of Zn1 in 3 with

labeling scheme. Symmetry codes: (A) −x, −y, −z; (B) x, y, z − 1; (C) −x + 1,
−y + 1, −z. (b) View of the 1D [Zn(5-NO2-1,3-BDC)]n chain in 3. (c) View of
the 2D [Zn2(5-NO2-1,3-BDC)2(1,4-bpetmb)]n network in 3. (d) View of the
Fig. 2 View of the 2D network of 2. The solvent MeCN molecules are 3D framework constructed by the 2D (4,4) networks of [Zn2(5-NO2-1,3-
highlighted in purple. All hydrogen atoms in the [Zn(5-Cl-1,3-BDC)(1,4- BDC)2(1,4-bpetmb)]n. The cyan, red and blue balls represent zinc, oxygen
bpetmb)]n network are omitted for clarity. The cyan, red, blue and green and nitrogen atoms, respectively. (e) View of topological net of 3. All
balls represent zinc, oxygen, nitrogen and chlorine atoms, respectively. hydrogen atoms are omitted for clarity.

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Crystal structure of 4
Compound 4 crystallizes in the monoclinic space group
P21/c, and the asymmetric unit contains one half of the
[Zn2(5-NH2-1,3-BDC)2(1,4-bpetmb)] unit and two solvent H2O
molecules. The Zn1 atom in 4 receives the contributions from
two O atoms belonging to the 5-NH2-1,3-BDC ligands, one
N atom belonging to the 5-NH2-1,3-BDC ligand and one
N atom belonging to the 1,4-bpetmb ligand, displaying a tet-
rahedral coordination geometry (Fig. 4a). The 5-NH2-1,3-BDC
ligands adopt a tridentate bridging mode with one coordinat-
ing amino group and two carboxyl groups. The Zn atoms are
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bridged by the tridentate 5-NH2-1,3-BDC ligands to give rise to

a 2D (6,3) layer of [Zn(5-NH2-1,3-BDC)]n extending in the bc
plane. Furthermore, the Zn atoms in two layers are connected
by 1,4-bpetmb ligands to form a 2D [Zn(5-NH2-1,3-BDC)(1,4-
bpetmb)]n network with 1D channels that runs along the b axis
(Fig. 4c). Calculation of the void volume for 4 by PLATON
analysis revealed a pore-accessible volume of 12.5% with
respect to the whole unit cell volume (247.5 Å3 out of the
1975.3 Å3 per unit cell volume), and the solvent H2O mole-
cules occupy the free void spaces in the channels. PXRD anal-
ysis indicated that the framework of 4 is maintained after
desolvation (Fig. S2d, ESI†). In order to examine the perma-
nent porosity of 4, we also attempted to investigate its gas
adsorption properties. However, the gas uptake of both N2
and CO2 were negligible (Fig. S3, ESI†). The results were
greatly affected by the methyl groups in the middle of the
channels of 4. These methyl groups divided each channel
into two equivalent parts. The window size of each part is
only about 2.81 × 3.54 Å2. Owing to the relative small window
size, the N2 and CO2 molecules could not access the chan-
nels. From the topological viewpoint, each Zn center can be
considered as a 4-connected node and each 5-NH2-1,3-BDC
ligand can be regarded as a 3-connected node. Thus, the
whole structure of 4 can be simplified as a 2D (3,4)-connected
network with a Schläfli symbol of (63)(65·8) (Fig. 4d).

Crystal structure of 5
Compound 5 crystallizes in the monoclinic space group P21/c,
and the asymmetric unit contains one [Zn2(μ-OH)(1,3,5-BTC)
(1,4-bpetmb)] unit. Single crystal X-ray crystallography
revealed that the two zinc atoms Zn1 and Zn2 adopt the simi-
lar coordination mode. Both of the tetrahedral Zn atoms are Fig. 4 (a) View of the coordination environment of Zn1 in 4 with
bonded to one O atom from the hydroxyl group, two O atoms labeling scheme. (b) View of the 2D (6,3) layer of [Zn(5-NH2-1,3-BDC)]n
from two different 1,3,5-BTC ligands and one N atom from in 4. (c) View of whole 2D network of 4. The solvent H2O molecules
are highlighted in purple. (d) View of the topological net of 4. All
the 1,4-bpetmb ligand (Fig. 5a). In 5, each pair of zinc atoms is hydrogen atoms are omitted for clarity. The cyan, red and blue balls
separated by one hydroxyl group to form a [Zn2(μ-OH)] unit. represent zinc, oxygen and nitrogen atoms, respectively. Symmetry
The adjacent [Zn2(μ-OH)] units are linked by three tridentate BTC codes: (A) −x, −y + 3, −z; (B) x, −y + 3/2, z − 1/2; (C) x, −y + 1/2, z − 1/2.
ligands to give rise to a 2D (6,3) net of [Zn2(μ-OH)(1,3,5-BTC)]n
(Fig. 5b). Furthermore, the unsaturated Zn atoms in the 2D
[Zn2(μ-OH)(1,3,5-BTC)]n nets are filled by the N atoms from single network has large channels, its void space is filled by
1,4-bpetmb ligands and finally afforded a 3D framework with mutual interpenetration of a crystallographic equivalent
1D channels that runs along the a axis. The shape of each net, generating a two-fold interpenetrating 3D architecture
channel is a triangular prism. The size for the window of (Fig. 5c). If the 1,3,5-BTC ligands and [Zn 2(μ-OH)] units
each channel is about 8.253 × 9.038 × 9.225 Å3. Although the are considered as 3- and 5-connecting nodes, the whole

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framework can be simplified as a (3,5)-connected network.

The Schläfli symbol for this network is (63)(67·83). It is noted
that the methyl groups in 1,4-bpetmb also play important
roles in determining the structure of 5. If the dipyridyl ligand
was replaced by 1,4-bpeb in this system, one carboxylic group
in 1,3,5-H3BTC would not be deprotonated.9d As a result, the
structural motif of the product [Zn(1,3,5-HBTC)(1,4-bpeb)]n is
absolutely different from that of 5.9d

Thermal and photoluminescence properties

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To characterize the framework stabilities of the five com-

plexes, thermogravimetric analyses (TGA) of complexes 1–5
were studied (ESI,† Fig. S5). Complex 1 is stable up to 308 °C.
The remaining weight (14.76%) corresponds to the percent-
age of ZnO (calcd 14.28%). Compound 2 exhibits an initial
weight loss of 3.65% in the range 30–170 °C, corresponding
to the loss of uncoordinated MeCN molecules (calcd 3.26%).
2 began to decompose at 278 °C. After decomposition, the
residue of ZnO remained (obsd 12.91%, calcd 13.02%). Com-
plex 3 shows no weight loss and is found to be stable up to
281 °C. Upon further heating, 3 decomposed gradually. The
residue is assumed to be ZnO (obsd 18.73%, calcd 18.30%).
For compound 4, a gradual weight loss between 30 and
150 °C is attributed to the release of lattice water molecules
(obsd 7.87%, calcd 7.99%). The further weight loss indicates
the decomposition of the framework from 393 °C. Finally,
the ZnO residue of 17.82% (calcd, 18.06%) is observed. The
TG analysis for compound 5 shows that the whole architec-
ture begins to decompose from 292 °C. The remaining weight
of 22.93% corresponds roughly to the deposition of ZnO
(calcd, 23.41%).
Luminescence properties of coordination polymers with
d10 metal centers have attracted long-standing interest, owing
to their various applications in chemical sensors, light emit-
ting diodes (LEDs) and electrochemical displays.1,12 Hence,
in this work, the photoluminescence properties of complexes

Fig. 5 (a) View of the coordination environments of Zn1 and Zn2 in 5 with
labeling scheme. Symmetry codes: (A) x, −y + 1/2, z − 1/2; (B) x, −y + 3/2, z − 1/2;
(C) x + 1, y − 1, z. (b) View of the 2D (6,3) net of [Zn2(μ-OH)(1,3,5-BTC)]n in
5. The cyan and red balls represent zinc and oxygen atoms, respectively.
(c) View of the two-fold interpenetrating 3D framework of 6. (d) View of Fig. 6 Solid state emission spectra of 1,4-bpetmb and 1–5 at ambient
the topological net of 5. All hydrogen atoms are omitted for clarity. temperature.

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