Effect of organic anions on the self-assembly of Zn(ii)-containing coordination polymers based on trigonal N-donor ligands

Article abstract of DOI:10.1039/c2ce25907a

A series of coordination polymers, namely, [Zn(2,3′-tmbpt)(o-bdc) (H₂O)] (1), [Zn(2,3′-tmbpt)(m-bdc)] (2), [Zn(2,3′-tmbpt) (p-bdc)]·H₂O (3), [Zn₂(2,3′-tmbpt)(btc)(OH)] ·0.5H₂O (4), [Zn(2,3′-tmbpt)(btec)_0.5] ·2H₂O (5), [Zn(3,3′-tmbpt)(o-bdc)]·H₂O (6), [Zn(3,3′-tmbpt)(m-bdc)(H₂O)]·H₂O (7), and [Zn₂(3,3′-tmbpt)(btc)(OH)(H₂O)] (8), where 2,3′-tmbpt = 1-((1H-1,2,4-triazol-1-yl)methyl)-3-(3-pyridyl)-5-(2-pyridyl) -1,2,4-triazole, 3,3′-tmbpt = 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3- pyridyl)-1,2,4-triazole, o-H₂bdc = 1,2-benzenedicarboxylic acid, m-H₂bdc = 1,3-benzenedicarboxylic acid, p-H₂bdc = 1,4-benzenedicarboxylic acid, H₃btc = 1,3,5-benzenetricarboxylic acid, and H₄btec = 1,2,4,5-benzenetetracarboxylic acid, have been synthesized under hydrothermal conditions. The structures of 1-8 have been determined by single-crystal X-ray diffraction analyses and were further characterized by infrared spectroscopy (IR), elemental analyses and powder X-ray diffraction (PXRD) analyses. Compounds 1 and 6 display 1D chain structures. Compound 2 shows a 3D 2-fold interpenetrating CdSO₄ framework. Compound 3 reveals a 2D 2-fold interpenetrating square layer (sql) structure. Compound 4 exhibits a 3D 2-fold interpenetrating framework with (6 ³)(6⁹·8) topology. Compound 5 shows a non-interpenetrating 3D framework with (8³)(8⁵·10) topology. Compound 7 has a 2D layer structure. Compound 8 displays a 3D 2-fold interpenetrating framework with (4·6²)(4²· 6⁸·8⁵) topology. The structural discrepancies of compounds 1-8 imply that the organic anions play an important role in the formation of the resultant structures of the coordination polymers. The luminescent properties of compounds 1-8 have also been investigated. This journal is

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PAPER
Effect of organic anions on the self-assembly of Zn(II)-containing
coordination polymers based on trigonal N-donor ligands{
Wei-Qiu Kan, Jin Yang,* Ying-Ying Liu and Jian-Fang Ma*
Received 7th June 2012, Accepted 24th July 2012
DOI: 10.1039/c2ce25907a
A series of coordination polymers, namely, [Zn(2,39-tmbpt)(o-bdc)(H2O)] (1),
[Zn(2,39-tmbpt)(m-bdc)] (2), [Zn(2,39-tmbpt)(p-bdc)]?H2O (3), [Zn2(2,39-tmbpt)(btc)(OH)]?0.5H2O
(4), [Zn(2,39-tmbpt)(btec)0.5]?2H2O (5), [Zn(3,39-tmbpt)(o-bdc)]?H2O (6),
[Zn(3,39-tmbpt)(m-bdc)(H2O)]?H2O (7), and [Zn2(3,39-tmbpt)(btc)(OH)(H2O)] (8), where 2,39-tmbpt
= 1-((1H-1,2,4-triazol-1-yl)methyl)-3-(3-pyridyl)-5-(2-pyridyl)-1,2,4-triazole, 3,39-tmbpt = 1-
((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole, o-H2bdc = 1,2-benzenedicarboxylic
acid, m-H2bdc = 1,3-benzenedicarboxylic acid, p-H2bdc = 1,4-benzenedicarboxylic acid, H3btc =
1,3,5-benzenetricarboxylic acid, and H4btec = 1,2,4,5-benzenetetracarboxylic acid, have been
synthesized under hydrothermal conditions. The structures of 1–8 have been determined by single-
crystal X-ray diffraction analyses and were further characterized by infrared spectroscopy (IR),
elemental analyses and powder X-ray diffraction (PXRD) analyses. Compounds 1 and 6 display 1D
chain structures. Compound 2 shows a 3D 2-fold interpenetrating CdSO4 framework. Compound 3
reveals a 2D 2-fold interpenetrating square layer (sql) structure. Compound 4 exhibits a 3D 2-fold
interpenetrating framework with (63)(69?8) topology. Compound 5 shows a non-interpenetrating 3D
framework with (83)(85?10) topology. Compound 7 has a 2D layer structure. Compound 8 displays a
3D 2-fold interpenetrating framework with (4?62)(42?68?85) topology. The structural discrepancies of
compounds 1–8 imply that the organic anions play an important role in the formation of the resultant
structures of the coordination polymers. The luminescent properties of compounds 1–8 have also
been investigated.
properties.6,7 In our previous work, we have reported a series of
Introduction
fascinating 3D highly connected frameworks based on three
structurally related trigonal N-donor ligands 1-((1H-1,2,4-triazol-1-
yl)methyl)-3,5-bis(4-pyridyl)-1,2,4-triazole (4,49-tmbpt), 1-((1H-1,
2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole (3,39-tmbpt)
and 1-((1H-1,2,4-triazol-1-yl)methyl)-3-(3-pyridyl)-5-(4-pyridyl)-1,
2,4-triazole (3,49-tmbpt).9 In these compounds, the tmbpt ligands
exhibit merits of both rigid and flexible ligands, and can coordinate
with metal ions in diverse coordination modes.9
The rational design and assembly of coordination polymers are
of current interest due to their fascinating architectures and
potential applications in gas storage, luminescence, separation,
catalysis, drug delivery, and so on.1,2 Up to now, a number of
N-donor bridging ligands, such as 4,49-bipyridine (bpy),3 1,4-
bis(1,2,4-triazol-1-yl)butane (btb),4 1,4-bis(1H-1,2,4-triazol-1-
ylmethyl)benzene (bbtz),5 2,4,6-tri(pyridyl)-1,3,5-triazine (tptz),6
1,3,5-tris(1,2,4-imidazol-1-ylmethyl)-2,4,6-trimethyl benzene (ttb),7
and tetrakis(imidazol-1-ylmethyl)methane (tiym),8 have been
widely employed to construct coordination polymers with
fascinating architectures and interesting properties. Among
the various N-donor bridging ligands, trigonal N-donor ligands
have been proven to be good candidates for the construction of
coordination polymers with versatile topologies and functional
On the other hand, organic anions play an important role in
the formation of coordination polymers with fascinating
structures. In order to investigate the effects of organic anions
on the structures of the compounds based on the tmbpt ligands
(2,39-tmbpt and 3,39-tmbpt, Scheme 1), five structurally
related organic polycarboxylic acids (Scheme 1) were used
and a series of Zn(II)-containing coordination polymers, namely,
[Zn(2,39-tmbpt)(o-bdc)(H2O)] (1), [Zn(2,39-tmbpt)(m-bdc)] (2),
[Zn(2,39-tmbpt)(p-bdc)]?H2O (3), [Zn2(2,39-tmbpt)(btc)(OH)]?0.5H2O
(4), [Zn(2,39-tmbpt)(btec)0.5]?2H2O (5), [Zn(3,39-tmbpt)(o-bdc)]?H2O
(6), [Zn(3,39-tmbpt)(m-bdc)(H2O)]?H2O (7), and [Zn2(3,39-tmbpt)
(btc)(OH)(H2O)] (8), where 2,39-tmbpt = 1-((1H-1,2,4-triazol-1-
yl)methyl)-3-(3-pyridyl)-5-(2-pyridyl)-1,2,4-triazole, 3,39-tmbpt =
1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole,
Key Lab of Polyoxometalate Science, Department of Chemistry, Northeast
Normal University, Changchun 130024, People’s Republic of China.
E-mail: yangjinnenu@yahoo.com.cn (J. Yang);
jianfangma@yahoo.com.cn (J.-F. Ma);
Fax: +86-431-85098620 (J.-F. Ma)
{ Electronic supplementary information (ESI) available. CCDC refer-
ence numbers 892065–892072. For ESI and crystallographic data in CIF
or other electronic format see DOI: 10.1039/c2ce25907a
6934 | CrystEngComm, 2012, 14, 6934–6945
This journal is ß The Royal Society of Chemistry 2012

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Scheme 1 Organic ligands used in this work.
o-H2bdc = 1,2-benzenedicarboxylic acid, m-H2bdc = 1,3-
benzenedicarboxylic acid, p-H2bdc = 1,4-benzenedicarboxylic
acid, H3btc = 1,3,5-benzenetricarboxylic acid, and H4btec =
1,2,4,5-benzenetetracarboxylic acid, have been synthesized
under hydrothermal conditions. The structures and topologi-
cal analyses of these compounds, and the influence of the
anions on the structures of the coordination polymers have
been discussed. The photoluminescent properties of the
compounds have also been studied.
1588(s), 1560(s), 1481(w), 1417(s), 1404(s), 1325(w), 1313(w),
1274(m), 1145(w), 1125(w), 1089(w), 994(w), 889(w), 820(w),
767(w), 717(w), 645(w).
Synthesis of [Zn(2,39-tmbpt)(m-bdc)] (2). The preparation of 2
was similar to that of 1 except that m-H2bdc (0.017 g, 0.1 mmol)
was used instead of o-H2bdc. Colorless crystals of 2 were
obtained in 37% yield. Anal. Calcd for C23H16ZnN8O4 (Mr =
533.81): C, 51.75; H, 3.03; N, 21.00. Found: C, 51.68; H, 3.11; N,
21.11. IR (cm21): 3384(w), 3153(w), 3078(w), 1610(s), 1589(m),
1565(s), 1460(s), 1389(s), 1355(s), 1284(w), 1199(w), 1143(w),
1122(w), 1100(w), 1049(w), 996(w), 881(w), 831(w), 799(w),
761(w), 743(s), 728(s), 707(w), 670(w).
Experimental
Materials and methods
The 2,39-tmbpt and 3,39-tmbpt ligands were synthesized by the
procedures reported previously.9 All commercially available
chemicals and solvents were of analytical grade and used without
further purification. Elemental analyses (C, H and N) were
carried out with a Perkin-Elmer 240 elemental analyzer. The FT-
IR spectra of the compounds were measured in the range of
4000–400 cm21 on a Mattson Alpha-Centauri spectrometer. The
solid-state photoluminescent data were recorded on a Perkin-
Elmer FLS-920 spectrometer at room temperature. PXRD
measurements were collected on a Rigaku Dmax 2000 X-ray
diffractometer with graphite monochromatized Cu-Ka radiation
(l = 0.154 nm) and 2h varying from 5 to 50u. The experimental
PXRD patterns matched well with the corresponding computer-
simulated ones (Fig. S1 and S2 in the ESI{).
Synthesis of [Zn(2,39-tmbpt)(p-bdc)]?H2O (3). The preparation
of 3 was similar to that of 2 except that p-H2bdc (0.017 g,
0.1 mmol) was used instead of m-H2bdc. Colorless crystals of 3
were obtained in 41% yield. Anal. Calcd for C23H18ZnN8O5 (Mr
= 551.82): C, 50.06; H, 3.29; N, 20.31. Found: C, 50.18; H, 3.15;
N, 20.22. IR (cm21): 3140(w), 3074(w), 1604(s), 1568(m),
1534(w), 1506(s), 1459(m), 1388(s), 1358(s), 1314(w), 1278(m),
1206(w), 1144(w), 1127(w), 1101(w), 996(m), 954(w), 881(w),
821(w), 798(w), 667(w), 576(w).
Synthesis of [Zn2(2,39-tmbpt)(btc)(OH)]?0.5H2O (4). The pre-
paration of 4 was similar to that of 3 except that H3btc (0.014 g,
0.067 mmol) was used instead of p-H2bdc. Colorless crystals of 4
were obtained in 29% yield. Anal. Calcd for C24H17Zn2N8O7.5
(Mr = 668.20): C, 43.14; H, 2.57; N, 16.77. Found: C, 43.21; H,
2.67; N, 16.68. IR (cm21): 3446(w), 3118(w), 3043(w), 1624(s),
1570(s), 1446(m), 1420(m), 1370(s), 1286(w), 1222(w), 1170(w),
1141(w), 1100(w), 1040(w), 1004(w), 903(w), 808(w), 762(w),
745(w), 721(w), 694(w), 670(w).
Synthesis of [Zn(2,39-tmbpt)(o-bdc)(H2O)] (1). A mixture of
Zn(CH3COO)2?2H2O (0.022 g, 0.1 mmol), o-H2bdc (0.017 g,
0.1 mmol), 2,39-tmbpt (0.03 g, 0.1 mmol), NaOH (0.008 g,
0.2 mmol) and 8 mL water was sealed in a 15 mL Teflon reactor
and heated at 130 uC for 3 days. After cooling to ambient
temperature at a rate of 10 uC h21, colorless crystals of 1 were
obtained in 32% yield. Anal. Calcd for C23H18ZnN8O5 (Mr =
551.82): C, 50.06; H, 3.29; N, 20.31. Found: C, 49.95; H, 3.22; N,
20.15. IR (cm21): 3311(w), 3133(w), 3067(w), 3030(w), 1610(m),
Synthesis of [Zn(2,39-tmbpt)(btec)0.5]?2H2O (5). The prepara-
tion of 5 was similar to that of 4 except that H4btec (0.013 g,
0.05 mmol) was used instead of H3btc. Colorless crystals of
This journal is ß The Royal Society of Chemistry 2012
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5 were obtained in 22% yield. Anal. Calcd for C20H17ZnN8O6
(Mr = 530.79): C, 45.25; H, 3.23; N, 21.12. Found: C, 45.40; H,
3.27; N, 21.01. IR (cm21): 3481(w), 3138(w), 3033(w), 1617(s),
1571(s), 1558(s), 1485(w), 1423(s), 1347(s), 1320(s), 1271(m),
1201(w), 1118(w), 1011(w), 991(w), 937(w), 894(w), 868(w),
804(w), 747(w), 671(w), 567(w).
X-Ray crystallography
Single-crystal X-ray diffraction data were collected on an Oxford
Diffraction Gemini R Ultra diffractometer with graphite-
˚
monochromated Mo-Ka radiation (l = 0.71073 A) at 293 K.
Absorption corrections were performed using a multi-scan
technique. The structures of compounds 1–8 were solved by
the Direct Method of SHELXS-9710a and refined by full-matrix
least-squares techniques employing the SHELXL-97 program.10b
Non-hydrogen atoms of compounds 1–8 were refined with
anisotropic temperature parameters. The hydrogen atoms
attached to the carbon atoms were generated geometrically and
Synthesis of [Zn(3,39-tmbpt)(o-bdc)]?H2O (6). The preparation
of 6 was similar to that of 1 except that 3,39-tmbpt (0.03 g,
0.1 mmol) was used instead of 2,39-tmbpt. Colorless crystals of 6
were obtained in 35% yield. Anal. Calcd for C23H18ZnN8O5 (Mr
= 551.82): C, 50.06; H, 3.29; N, 20.31. Found: C, 50.16; H, 3.14;
N, 20.22. IR (cm21): 3503(w), 3138(w), 3034(w), 1617(s), 1557(s),
1423(s), 1341(m), 1320(m), 1291(w), 1271(w), 1201(w), 1118(w),
1089(w), 1011(w), 991(w), 937(w), 868(w), 823(w), 766(w),
747(w), 670(w).
˚
were refined using a riding model with d(C–H) = 0.93 A, Uiso
=
˚
1.2Ueq(C) for aromatic and d(C–H) = 0.97 A, Uiso = 1.2Ueq(C)
for CH2 atoms. The hydrogen atoms of water molecules and
hydroxyl group were located from difference Fourier maps
˚
and were refined as riding atoms with d(O–H) = 0.811–0.857 A
and Uiso = 1.5Ueq(O). In 4, the hydrogen atoms of O1W and
hydroxyl group (O7) were not included in the model. The
detailed crystallographic data and structure refinement para-
meters for 1–8 are listed in Table 1. Selected bond distances and
angles for the compounds are given in the Tables S1-S8{. The
topologies of the compounds were analyzed by the OLEX
program.11
Synthesis of [Zn(3,39-tmbpt)(m-bdc)(H2O)]?H2O (7). The pre-
paration of 7 was similar to that of 6 except that m-H2bdc
(0.017 g, 0.1 mmol) was used instead of o-H2bdc. Colorless
crystals of 7 were obtained in 41% yield. Anal. Calcd for
C23H20ZnN8O6 (Mr = 569.84): C, 48.48; H, 3.54; N, 19.67.
Found: C, 48.59; H, 3.47; N, 19.39. IR (cm21): 3384(m), 1614(s),
1559(s), 1481(w), 1442(m), 1416(s), 1376(s), 1272(w), 1199(w),
1151(w), 1127(w), 1075(w), 1012(w), 986(w), 953(w), 816(w),
784(w), 748(m), 725(w), 699(w), 670(w), 641(w).
Results and discussion
In this work, two trigonal N-donor ligands (2,39-tmbpt and
3,39-tmbpt) and five structurally related aromatic carboxylates
anions were used to investigate the effect of the organic anions
on the final structures of the compounds. The numbers and
positions of the carboxylate groups in the five organic anions are
different. Compounds 1–5 are based on Zn(II) ions, 2,39-tmbpt
ligands and distinct aromatic carboxylate anions (o-bdc, m-bdc,
p-bdc, btc and btec). However, compounds 6–8 are based on
Zn(II) ions, 3,39-tmbpt ligands and different aromatic carbox-
ylate anions (o-bdc, m-bdc and btc).
Synthesis of [Zn2(3,39-tmbpt)(btc)(OH)(H2O)] (8). The pre-
paration of 8 was similar to that of 7 except that H3btc (0.014 g,
0.067 mmol) was used instead of m-H2bdc. Colorless crystals of 8
were obtained in 38% yield. Anal. Calcd for C24H18Zn2N8O8 (Mr
= 677.20): C, 42.56; H, 2.68; N, 16.55. Found: C, 42.42; H, 2.55;
N, 16.44. IR (cm21): 3442(w), 3144(w), 3087(w), 1618(s), 1567(s),
1458(w), 1435(m), 1411(m), 1369(s), 1286(w), 1163(w), 1137(w),
1096(w), 1029(w), 989(w), 885(w), 820(w), 810(w), 722(w),
704(w), 669(w), 634(w).
Table 1 Crystal data and structure refinements for compounds 1–8
1
2
3
4
5
6
7
8
Formula
C23H18
N8O5Zn
551.82
Triclinic
¯
P1
8.9771(6)
11.0283(7)
12.0901(6)
74.718(5)
85.000(5)
81.608(6)
C
23H16
C
23H18
C
24H17
C20H17
N8O6Zn
530.79
C
23H18
C
23H20
C
24H18
N8O4Zn
533.81
Monoclinic
C2/c
22.1231(10) 10.8170(5)
12.5698(4)
18.1222(7)
90
109.511(5)
90
N8O5Zn
551.82
Triclinic
N8O7.5Zn2
668.20
Monoclinic Monoclinic
C2/c
25.9785(7)
10.1939(2)
19.4052(5)
90
101.070(3)
90
N8O5Zn
551.82
Triclinic
N8O6Zn
569.84
Monoclinic
P21/n
9.8552(3)
23.1468(8)
10.2245(4)
90
98.033(3)
90
N8O8Zn2
677.20
Monoclinic
C2/c
25.5723(13)
10.2646(3)
20.2916(9)
90
112.618(6)
90
Formula weight
Crystal system
Space group
¯
¯
P1
P21/c
P1
˚
a/A
11.8534(5)
15.0975(5)
12.5650(5)
90
111.268(5)
90
9.7186(5)
11.4928(6)
11.6881(6)
63.618(5)
80.197(5)
81.893(4)
˚
b/A
11.0298(7)
11.3773(6)
114.656(6)
104.715(4)
95.911(5)
1159.00(11) 5043.3(2)
2
1.581
564
˚
c/A
a (u)
b (u)
c (u)
3
˚
V/A
1140.77(12) 4750.1(3)
8
2095.45(14) 1149.29(10) 2309.49(14) 4916.7(4)
2
Z
2
8
4
4
8
Dc/g cm23
F(000)
1.607
564
1.493
2176
1.760
2696
1.682
2168
1.595
564
1.639
1168
1.830
2736
Reflections (collected/unique)
Rint
7062/4154
0.0353
9070/4340
0.0310
1.026
0.0360
0.0745
7289/4214
0.0308
1.036
0.0469
0.1096
9907/4610
0.0263
1.026
0.0432
0.1039
7768/3822
0.0295
1.041
0.0414
0.1053
7529/4189
0.0497
1.016
0.0565
0.1093
9048/4215
0.0412
1.015
0.0474
0.0804
8998/4493
0.0455
1.010
0.0443
0.0777
Goodness-of-fit (GOF) on F2 1.057
R1a[I . 2s(I)]
wR2b[I . 2s(I)]
a
0.0418
0.0838
b
R1 = g||Fo| 2 |Fc||/g|Fo|. wR2 = |gw(|Fo|2 2 |Fc|2)|/g|w(Fo2)2|1/2
.
6936 | CrystEngComm, 2012, 14, 6934–6945
This journal is ß The Royal Society of Chemistry 2012

View Online
Structure of [Zn(2,39-tmbpt)(o-bdc)(H2O)] (1)
Compound 1 displays a 1D chain structure. The asymmetric unit
of 1 consists of one Zn(II) ion, one 2,39-tmbpt ligand, one o-bdc
anion and one coordinated water molecule. As shown in Fig. 1a,
each Zn(II) ion is five-coordinated in a distorted trigonal
bipyramid coordination geometry, defined by two nitrogen
atoms from two individual 2,39-tmbpt ligands [Zn1–N1 =
2.091(2) and Zn1–N7#2 = 2.215(2) A] and three oxygen atoms
˚
from two distinct o-bdc anions and one coordinated water
molecule [Zn1–O1 = 1.988(2), Zn1–O3#1 = 1.999(2) and Zn1–
˚
O1W = 2.179(2) A]. Each 2,39-tmbpt ligand acts as a bidentate
ligand with the free 2-position pyridyl group. A pair of
2,39-tmbpt ligands link two Zn(II) ions to form a closed loop.
The two carboxylate groups of the o-bdc anions in a m1-g1: g0
coordination mode (mode I in Scheme S1, ESI{) further connect
the neighboring loops in pairs to generate a 1D chain (Fig. 1b).
…
Moreover, there are intermolecular O–H O hydrogen-bond-
ing interactions between water molecules and the carboxylate
oxygen atoms (Table S1b{). The chains of 1 are extended by the
hydrogen-bonding interactions to generate a 2D supramolecular
layer (Fig. S3 in ESI{).
Structure of [Zn(2,39-tmbpt)(m-bdc)] (2)
Compound 2 shows a 3D 2-fold interpenetrating framework
with CdSO4 topology. The asymmetric unit of 2 contains one
Zn(II) ion, one 2,39-tmbpt ligand and one m-bdc anion. As
shown in Fig. 2a, each Zn(II) ion is four-coordinated by two
nitrogen atoms from two different 2,39-tmbpt ligands (Zn1–N1 =
2.042(2) and Zn1–N8#2 = 2.044(2) A) and two oxygen atoms
˚
from two individual m-bdc anions (Zn1–O1 = 1.984(2) and Zn1–
O4#1 = 1.942(2) A) in a tetrahedral coordination geometry. Each
˚
2,39-tmbpt ligand behaves as a bidentate ligand with the free
2-position pyridyl group. In this way, the 2,39-tmbpt ligands link
the Zn(II) ions to form a wave like chain (Fig. 2b). The two
carboxylate groups of the m-bdc anion adopt a m1-g1:g0
coordination mode (mode II in Scheme S1, ESI{). In this way,
Fig. 2 (a) ORTEP view of 2 showing the local coordination environ-
ment of Zn(II) ion with hydrogen atoms omitted for clarity (30%
#1
probability displacement ellipsoids). Symmetry codes: x, 2y, z 2 1/2;
#2 x 2 1/2, y 2 1/2, z. (b) View of the 1D chain constructed by Zn(II) ions
and 2,39-tmbpt ligands. (c) View of the 3D framework of 2. (d) View of
the 3D 2-fold interpenetrating framework of 2.
the neighboring chains are further linked by the m-bdc anions to
yield a 3D framework (Fig. 2c).
Topologically, if the Zn(II) ions can be considered as
4-connected nodes, and the 2,39-tmbpt ligands and the m-bdc
anions are viewed as linkers, the 3D framework of 2 can be
simplified as a 4-connected net with (65?8) CdSO4-type topology.
Two identical nets interpenetrate each other, giving rise to a
2-fold interpenetrating framework (Fig. 2d).
Fig. 1 (a) ORTEP view of 1 showing the local coordination environ-
ment of Zn(II) ion with hydrogen atoms omitted for clarity (30%
probability displacement ellipsoids). Symmetry codes: #1 2x + 1, 2y + 1,
#2
2z;
2x, 2y, 2z + 1. (b) View of the 1D chain of 1.
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Structure of [Zn(2,39-tmbpt)(p-bdc)]?H2O (3)
Compound 3 exhibits a 2D 2-fold interpenetrating structure. The
asymmetric unit of 3 contains one Zn(II) ion, one 2,39-tmbpt
ligand, one p-bdc anion and one lattice water molecule. As
shown in Fig. 3a, each Zn(II) ion is four-coordinated in a
tetrahedral coordination geometry, completed by two nitrogen
atoms from two distinct 2,39-tmbpt ligands (Zn1–N1 = 2.026(3)
and Zn1–N7#1 = 2.059(3) A) and two oxygen atoms from two
˚
different p-bdc anions (Zn1–O1 = 1.954(3) and Zn1–O3 =
˚
1.941(2) A). Each 2,39-tmbpt ligand acts as a bidentate ligand
with the free 2-position pyridyl group. The 2,39-tmbpt ligands
bridge the Zn(II) ions to form a 1D chain. The two carboxylate
groups of the p-bdc anion adopt a m1-g1: g0 coordination mode
(mode III in Scheme S1, ESI{). In this manner, the neighboring
chains are then linked by the p-bdc anions to yield a wave like
layer (Fig. 3b). Further, two networks interlock each other to
generate a 2D 2-fold interpenetrating network (Fig. 3c). In
addition, there is intramolecular hydrogen-bonding interaction
between O1W and O2 of the carboxylate group, which further
stabilizes the layer of 3 (Fig. S4 and Table S3b{).
Topologically, if the Zn(II) ions are regarded as 4-connected
nodes, and the 2,39-tmbpt ligands and the p-bdc anions are
simplified as linkers, the layer can be described as a 2D sql
network with (44?62) topology.
Structure of [Zn2(2,39-tmbpt)(btc)(OH)]?0.5H2O (4)
Compound 4 has a 3D 2-fold interpenetrating framework with
(63)(69?8) topology. The asymmetric unit of 4 consists of two
Zn(II) ions, one 2,39-tmbpt ligand, one btc anion, one hydroxyl
group, and half a lattice water molecule. As shown in Fig. 4a,
Zn1 and Zn2 show similar tetrahedral coordination geometries,
completed by one nitrogen atom from one 2,39-tmbpt ligand
(Zn1–N1 = 2.018(3) and Zn2–N7#3 = 2.070(3) A) and three
˚
oxygen atoms from two different btc anions and one hydroxyl
group (Zn1–O7 = 1.925(3), Zn1–O3#1 = 1.959(2), Zn1–O6#2
=
2.017(3), Zn2–O1 = 1.925(3), Zn2–O7 = 1.920(3) and Zn2–O5#2
˚
= 1.928(3) A). Zn1 and Zn2 ions are held together by the
hydroxyl group to form a binuclear unit [Zn2O]. The carboxylate
groups of the btc anion in m1-g1:g0 and m2-g1:g1 coordination
modes (mode IV in Scheme S1, ESI{) further connect the
binuclear units to generate a 2D layer (Fig. 4b). Each 2,39-tmbpt
ligand, as a bidentate ligand with the free 2-position pyridyl
group, links the neighboring layers to yield a 3D framework
(Fig. 4c). Two identical nets interpenetrate each other to form a
Fig. 3 (a) ORTEP view of 3 showing the local coordination environ-
ment of Zn(II) ion with hydrogen atoms and lattice water molecules
omitted for clarity (30% probability displacement ellipsoids). Symmetry
codes: #1 x, y + 1, z + 1; #2 2x + 1, 2y + 1, 2z; #3 2x + 1, 2y, 2z + 1.
(b) View of the 2D layer formed by Zn(II) ions, 2,39-tmbpt ligands and
p-bdc anions. (c) View of the 2-fold interpenetrating sql network.
…
2-fold interpenetrating framework. There are O–H O hydro-
gen-bonding interactions between the lattice water molecule and
the carboxylate oxygen atoms, which consolidate the whole
2-fold interpenetrating framework (Fig. S5 and Table S4b{).
Topologically, if the binuclear units [Zn2O] are considered as
5-connected nodes, the btc anions are viewed as 3-connected
nodes, and the 2,39-tmbpt ligands are regarded as linkers, the 3D
framework can be simplified as a (3,5)-connected framework
with (63)(69?8) topology (Fig. 4d).
Zn(II) ion, one 2,39-tmbpt ligand, one btec anion, and two lattice
water molecules. As shown in Fig. 5a, each Zn(II) ion is four-
coordinated by two nitrogen atoms from two individual
2,49-tmbpt ligands (Zn1–N1 = 2.040(3) and Zn1–N8#2
=
˚
2.050(3) A) and two oxygen atoms from two distinct btec anions
(Zn1–O1 = 1.931(2) and Zn1–O3#1 = 1.959(2) A) in a tetrahedral
˚
Structure of [Zn(2,39-tmbpt)(btec)0.5]?2H2O (5)
coordination geometry. The carboxylate groups of the btec
anion in a m1-g1:g0 coordination mode (mode V in Scheme S1,
ESI{) links the Zn(II) ions to form a layer (Fig. 5b). Each
Compound 5 shows a 3D (3,4)-connected framework with
(83)(85?10) topology. The asymmetric unit of 5 contains one
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Fig. 5 (a) ORTEP view of 5 showing the local coordination environ-
ment of Zn(II) ion with hydrogen atoms and lattice water molecules
omitted for clarity (30% probability displacement ellipsoids). Symmetry
codes: #1 x, 2y + 1/2, z 2 1/2; #2 2x + 1, 2y, 2z; #3 2x + 2, 2y + 1, 2z.
(b) View of the layer formed by Zn(II) ions and btec anions. (c) View of
the 3D framework of 5. (d) Schematic view of the 3D (3,4)-connected
framework of 5 with (83)(85?10) topology.
Fig. 4 (a) ORTEP view of 4 showing the local coordination environments of
Zn(II) ions with hydrogen atoms and lattice water molecules omitted for clarity
(30% probability displacement ellipsoids). Symmetry codes: #1 x, 2y, z + 1/2; #2
x, 2y + 1, z + 1/2; #3 x 2 1/2, y + 1/2, z. (b) View of the layer formed by Zn(II)
ions, hydroxyl groups and btc anions. (c) View of the 3D framework of 4. (d)
View of the 3D 2-fold interpenetrating framework of 4 with (63)(69?8) topology.
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2,39-tmbpt ligand acts as a bidentate ligand with the free
2-position pyridyl group. In this way, the 2,39-tmbpt ligands
further connected the layers in pairs to generate a 3D framework
…
(Fig. 5c). Furthermore, there are O–H O hydrogen-bonding
interactions between the lattice water molecules and the carboxy-
late oxygen atoms, which stabilize the whole 3D framework of 5
(Fig. S6 and Table S5b{).
Topologically, if the Zn(II) ions are regarded as 3-connected
nodes, the btec anions are considered as 4-connected nodes, and
the 2,39-tmbpt ligands are viewed as linkers, the 3D framework
of 5 can be described as a (3,4)-connected framework with
(83)(85?10) topology (Fig. 5d).
Structure of [Zn(3,39-tmbpt)(o-bdc)]?H2O (6)
Compound 6 exhibits a 1D chain structure. The asymmetric unit
of 6 consists of one Zn(II) ion, one 3,39-tmbpt ligand, one o-bdc
anion and one lattice water molecule. As shown in Fig. 6a, each
Zn(II) ion is four-coordinated by two nitrogen atoms from two
distinct 3,39-tmbpt ligands (Zn1-N1 = 2.050(3) and Zn1–N8#2
=
˚
2.116(3) A) and two oxygen atoms from two different o-bdc
anions (Zn1–O2 = 1.956(3) and Zn1–O3#1 = 1.959(3) A). Each
˚
3,39-tmbpt ligand acts as a bidentate ligand with the free
peripheral triazolyl group. A pair of 3,39-tmbpt ligands link two
Zn(II) ions to generate a closed loop. The two carboxylate groups
of the o-bdc anion adopt a m1-g1: g0 coordination mode (mode I
in Scheme S1, ESI{). In this way, neighboring loops are further
linked by the o-bdc anions into a 1D chain (Fig. 6b). Moreover,
…
…
there are intramolecular O–H O and O–H N hydrogen-
bonding interactions, which further consolidate the 1D chain
(Fig. S7 and Table S6b in ESI{).
Structure of [Zn(3,39-tmbpt)(m-bdc)(H2O)]?H2O (7)
Compound 7 has a 2D layer structure. The asymmetric unit of 7
consists of one Zn(II) ion, one 3,39-tmbpt ligand, one m-bdc
anion and two water molecules. As shown in Fig. 7a, each Zn(II)
Fig. 7 (a) ORTEP view of 7 showing the local coordination environ-
ment of Zn(II) ion with hydrogen atoms and lattice water molecules
omitted for clarity (30% probability displacement ellipsoids). Symmetry
codes: #1 x, y, z + 1; #2 x 2 1/2, 2y + 1/2, z + 1/2. (b) View of the meso-
helix chain constructed by Zn(II) ions, 3,39-tmbpt ligands and m-bdc
anions. (c) View of the 2D layer of 7.
Fig. 6 (a) ORTEP view of 6 showing the local coordination environ-
ment of Zn(II) ion with hydrogen atoms and lattice water molecules
omitted for clarity (30% probability displacement ellipsoids). Symmetry
codes: #1 2x + 1, 2y, 2z; #2 2x + 2, 2y + 1, 2z 2 1. (b) View of the 1D
chain of 6.
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ion is five-coordinated by two nitrogen atoms from two different
3,39-tmbpt ligands (Zn1–N1 = 2.157(2) and Zn1–N8#2 = 2.217(3)
˚
A) and three oxygen atoms from two individual m-bdc anions
and one water molecule (Zn1–O2 = 2.042(2), Zn1–O4#1
=
˚
2.057(2) and Zn1–O1W = 2.082(2) A) in a trigonal bipyramid
coordination geometry. Each 3,39-tmbpt ligand serves as a
bidentate ligand with one of the free 3-position pyridyl group. In
this way, the 3,39-tmbpt ligands bridge the Zn(II) ions to form a
single-stranded meso-helical chain (Fig. 7b). Notably, the meso-
helix chain, having alternating right and left turns of the strand,
is not a helical structure, because the strand contains inversion
centers and does not have chirality.12 The two carboxylate
groups of the m-bdc anion adopt a m1-g1:g0 coordination mode
(mode II in Scheme S1, ESI{). In this fashion, adjacent chains
are further bridged by the m-bdc anions to form a layer (Fig. 7c).
…
In addition, there are intermolecular O–H O and O–H
…
N
hydrogen-bonding interactions, which led the layers to a 3D
supramolecular architecture (Fig. S8 in ESI{).
Structure of [Zn2(3,39-tmbpt)(btc)(OH)(H2O)] (8)
Compound 8 displays a 3D 2-fold interpenetrating framework.
The asymmetric unit of 8 contains two Zn(II) ions, one
3,39-tmbpt ligand, one btc anion, one hydroxyl group and one
coordinated water molecule. As shown in Fig. 8a, both Zn1 and
Zn2 are five-coordinated in trigonal bipyramid coordination
geometries, but their coordination environments are entirely
different. Zn1 is coordinated by two nitrogen atoms from two
different 3,39-tmbpt ligands (Zn1–N1 = 2.100(4) and Zn1–N7#3
˚
= 2.167(4) A) and three oxygen atoms from two btc anions and
one hydroxyl group (Zn1–O1 = 2.056(3), Zn1–O4#2 = 2.095(2),
Zn1–O7#1 = 1.954(2) A). Zn2 is coordinated by one nitrogen
˚
atom from one 3,39-tmbpt ligand (Zn2–N8#5 = 2.280(4) A) and
˚
four oxygen atoms from two individual btc anions, one hydroxyl
group and one water molecule (Zn2–O5 = 1.939(3), Zn2–O7 =
1.913(2), Zn2–O3#4 = 1.977(3) and Zn2–O1W = 2.288(3) A). Zn1
˚
and Zn2 ions are held together by one hydroxyl group to form a
binuclear unit [Zn2O]. Each 3,39-tmbpt ligand, as a tridentate
ligand, links the binuclear units to generate a 1D chain (Fig. 8b).
The carboxylate groups of the btc anion adopt m1-g1:g0 and m2-
g1:g1 coordination modes, respectively (mode IV in Scheme S1,
ESI{). In this manner, neighboring chains are further joined
together by the btc anions to yield a 3D framework (Fig. 8c).
Topologically, if the binuclear units [Zn2O] are considered as
6-connected nodes, and the btc anions and the 3,39-tmbpt ligands
are viewed as 3-connected nodes, the 3D framework can be
simplified as a (3,6)-connected framework with (4?62)(42?68?85)
topology. Two identical (3,6)-connected nets interlock each
other, giving rise to a 3D 2-fold interpenetrating framework
(Fig. 8d).
Fig. 8 (a) ORTEP view of 8 showing the local coordination environ-
ments of Zn(II) ions with hydrogen atoms omitted for clarity (30%
#1
probability displacement ellipsoids). Symmetry codes: x, 2y, z 2 1/2;
#2 x, y + 1, z; #3 x + 1/2, 2y + 1/2, z + 1/2; #4 x, 2y 2 1, z + 1/2; #5 x + 1/
2, 2y 2 1/2, z + 1/2. (b) View of the chain formed by Zn(II) ions,
hydroxyl groups and 3,39-tmbpt ligands. (c) View of the 3D framework
of 8. (d) Schematic view of the 2-fold interpenetrating framework of 8.
Effect of the organic anions on the structures of the compounds
Compounds [Zn(2,39-tmbpt)(o-bdc)(H2O)] (1), [Zn(2,39-tmbpt)
(m-bdc)] (2), and [Zn(2,39-tmbpt)(p-bdc)]?H2O (3), as well as
[Zn(3,39-tmbpt)(o-bdc)]?H2O (6) and [Zn(3,39-tmbpt)(m-bdc)
(H2O)]?H2O (7), show the effect of the positions of the carboxylate
groups on the structures. Take compounds 1–3 for example.
Although the o-bdc, m-bdc and p-bdc anions serve as dicarbox-
ylate anions with the rigid benzene ring spacers, the positions and
It is well known that the organic anions play an important role in
determining the final structures of the compounds. By varying
the anions under similar synthetic conditions eight related Zn(II)
compounds with different structures were successfully synthe-
sized. The roles played by the carboxylate anions in compounds
1–8 can be explained in terms of their differences in the positions
and numbers of the carboxylate groups.
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Fig. 9 Solid-state excitation (blue) and emission (black) spectra of 2,39-tmbpt and compounds 1–5 at room temperature.
angles of the two carboxylate groups are entirely different. In the
o-bdc and m-bdc anions, the two carboxylate groups are located in
the 1,2- and 1,3-positions with the angles of 60u and 120u,
respectively, whereas in the p-bdc anion, the two carboxylate
groups are in the 1,4-positions with the angle of 180u. The
different angles between the two carboxylate groups in o-bdc,
m-bdc and p-bdc anions led to their coordination with the Zn(II)
ions in different directions, which further results in different
Zn(II)-carboxylate motifs in 1–3. In 1, a pair of o-bdc anions link
two Zn(II) ions to generate a closed loop. Neighboring loops are
further extended by the 2,39-tmbpt ligands into a chain. In 2, each
m-bdc anion bridges two Zn(II) ions to form slightly undulated
chains, which are further linked by the 2,39-tmbpt ligands into a
3D 2-fold interpenetrating framework. However, in 3, each p-bdc
anion bridges two Zn(II) ions to form highly undulated chains,
which are further connected by the 2,39-tmbpt ligands to form a
2D 2-fold interpenetrating network. It is clear that the position
discrimination of the carboxylate groups leads to the structural
difference of compounds 1–3.
Compounds [Zn2(2,39-tmbpt)(btc)(OH)]?0.5H2O (4) and
[Zn(2,39-tmbpt)(btec)0.5]?2H2O (5) exhibit the effect of the
number of the carboxylate groups on the resultant structures.
Compared with btc, the btec anion has an extra carboxylate
group. Usually, the additional carboxylate group can increase
the connection number of the ligand, which further results in
different structure motifs. In 4, each btc anion, as a 3-connected
node, links the Zn(II) ions to generate a planar layer, whereas, in
5, each btec anion, as a 4-connected node, bridges the Zn(II) ions
to yield a wave-like layer. The layers in 4 are further linked by
the 2,39-tmbpt ligands to form a 3D 2-fold interpenetrating
framework, whereas, in 5, the layers are further connected by the
2,39-tmbpt ligands to furnish a 3D non-interpenetrating frame-
work. Obviously, the numbers of the carboxylate group show an
important influence on the structures of the compounds.
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Fig. 10 Solid-state excitation (blue) and emission (black) spectra of 3,39-tmbpt and compounds 6–8 at room temperature.
342 nm), 412/526 nm (lex = 342 nm) and 425/524 nm (lex
IR spectra
=
335 nm), respectively. These emissions should originate from the
3,39-tmbpt ligand, because similar peaks also appear for the free
3,39-tmbpt ligand.19
The bands in the range of 3030–3503 cm21 are assigned to the
OH stretching modes of the water molecules for the complex-
es.13a The asymmetric and symmetric stretching vibrations of
carboxylate groups are observed in the ranges of 1506–1624 and
1313–1485 cm21, respectively.13a–c The absence of the characteris-
tic bands at around 1700 cm21 in the compounds indicates the
complete deprotonation of the carboxylic groups upon reaction
with Zn(II) ions.13a–c The peaks observed from 1201 to 1286 cm21
are assigned to the triazole ring vibration.13d
The luminescence decay curves of 1–8 at room temperature
(Figs. S9 and S10 in ESI{) fit well into a double-exponential
function as I = A + B1 6 exp(2t/t1) + B2 6 exp(2t/t2). The
emission decay lifetimes are t1 = 3.94 ns (59.85%) and t2
=
16.54 ns (40.15%) (x2 = 1.024) for 1, t1 = 2.81 ns (28.52%) and t2
= 11.61 ns (71.48%) (x2 = 1.000) for 2, t1 = 4.02 ns (39.80%) and
t2 = 14.19 ns (60.20%) (x2 = 1.027) for 3, t1 = 7.90 ns (35.42%)
and t2 = 25.09 ns (64.58%) (x2 = 1.173) for 4, t1 = 2.34 ns
(75.25%) and t2 = 8.45 ns (24.75%) (x2 = 1.007) for 5, t1 = 1.39 ns
(94.56%) and t2 = 5.95 ns (5.44%) (x2 = 1.006) for 6, t1 = 2.73 ns
(76.85%) and t2 = 7.92 ns (23.15%) (x2 = 1.006) for 7, and t1 =
2.73 ns (80.51%) and t2 = 9.47 ns (19.49%) (x2 = 1.000) for 8. The
luminescence lifetimes of 1–8 are much shorter than the ones
from a triplet state (.1023 s), so the emissions should arise from
the singlet state.20
Luminescent properties. Coordination polymers with d10
metals display interesting luminescent properties.14 The lumines-
cent properties of the free organic ligands and compounds 1–8
have been investigated in the solid state at room temperature
(Fig. 9 and 10).
The free 2,39-tmbpt, 3,39-tmbpt, o-H2bdc, m-H2bdc, p-H2bdc,
H3btc and H4btec show emission bands centered at 542 nm,
421/537 nm, 375 nm,15a 390 nm,15b 393 nm,15c 395 nm15d and
380 nm,15e respectively. The ligand emission peaks may be attri-
buted to the p *–n or p*–p transition as previously reported.16
Compounds 1–5 show emission bands at 410 nm (lex = 340 nm),
Conclusions
In summary, eight Zn(II)-containing coordination polymers
based on polycarboxylates and trigonal N-donor ligands have
been synthesized under hydrothermal conditions. These com-
pounds display various structure variations from 1D to 3D. The
diverse structures of the compounds reveal that the numbers and
positions of the carboxylate groups play important roles in the
formation of the final structures. The photoluminescent spectra
indicate that compounds 1–8 may be good candidates for optical
materials.
407 nm (lex = 337 nm), 417 nm (lex = 344 nm), 428 nm (lex
=
334 nm) and 410 nm (lex = 331 nm), respectively. These
emissions are probably due to the intraligand charge transi-
tions of the corresponding anions, since similar emission peaks
are observed for the organic polycarboxylic acids.17 The small
red shifts with respect to the anions may be assigned to
the coordination of carboxylate groups to the Zn(II) ions.18
The emission bands of compounds 6–8 are at 402/524 nm (lex
=
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7 (a) H. K. Liu, W. Y. Sun, W. X. Tang, T. Yamamoto and
N. Ueyama, Inorg. Chem., 1999, 38, 6313; (b) W. Y. Sun, J. Fan,
T. Okamura, J. Xie, K. B. Yu and N. Ueyama, Chem.–Eur. J., 2001,
7, 2557; (c) J. Fan, H. F. Zhu, T. Okamura, W. Y. Sun, W. X. Tang
and N. Ueyama, Chem.–Eur.J., 2003, 9, 4724; (d) J. Fan, H. F. Zhu,
T. Okamura, W. Y. Sun, W. X. Tang and N. Ueyama, Inorg. Chem.,
2003, 42, 158; (e) H. K. Liu and X. J. Tong, Chem. Commun., 2002,
1316; (f) Z. H. Zhang, Y. Song, T. Okamura, Y. Hasegawa, W. Y.
Sun and N. Ueyama, Inorg. Chem., 2006, 45, 2896.
8 (a) H. Y. Bai, J. F. Ma, J. Yang, Y. Y. Liu, H. Wu and J. C. Ma,
Cryst. Growth Des., 2010, 10, 995; (b) H. Y. Bai, J. F. Ma, J. Yang,
L. P. Zhang, J. C. Ma and Y. Y. Liu, Cryst. Growth Des., 2010, 10,
1946; (c) H. Y. Bai, J. F. Ma, J. Yang, B. Liu, L. P. Zhang, J. C. Ma
and Y. Y. Liu, Eur. J. Inorg. Chem., 2010, 5709; (d) H. Y. Bai,
J. Yang, B. Liu, J. F. Ma, W. Q. Kan, Y. Y. Liu and Y. Y. Liu,
Chem. Rev., 2011, 13, 5877.
Acknowledgements
We thank the National Natural Science Foundation of China
(grant nos. 21071028, 21001023), the Science Foundation of Jilin
Province (201215005, 20100109), the Fundamental Research
Funds for the Central Universities, the Specialized Research
Fund for the Doctoral Program of Higher Education, and the
Training Fund of NENU’s Scientific Innovation Project.
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