Zn(II) - American Chemical Society

DOI: 10.1021/cg100139p

Zn(II) and Cd(II) Coordination Polymers Assembled from a Versatile Tecton 5-Nitro-1,2,3-benzenetricarboxylic Acid and N,N0 -Donor Ancillary Coligands

2010, Vol. 10 2641–2649

Lu-Fang Ma,† Cheng-Peng Li,‡ Li-Ya Wang,*,† and Miao Du*,‡ †

College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, P. R. China, and ‡College of Chemistry and Life Science, Tianjin Key Laboratory of Structure and Performance for Functional Molecule, Tianjin Normal University, Tianjin 300387, P. R. China Received January 29, 2010; Revised Manuscript Received April 17, 2010

ABSTRACT: Five novel zinc(II) and cadmium(II) metal-organic coordination polymers with a tricarboxyl tecton and N-donor ancillary ligands, {[Zn(Hnbta)(2,20 -bipy)] 3 H2O}n (1), {[Cd3(nbta)2(2,20 -bipy)2(H2O)2]}n (2), {[Cd3(nbta)2(bpa)2]}n (3), {[Zn2(nbta)(OH)(bpa)1.5] 3 2H2O}n (4), and {[Zn3(nbta)2(bpp)2(H2O)2]}n (5) (H3nbta = 5-nitro-1,2,3-benzenetricarboxylic acid, 2,20 -bipy = 2,20 -bipyridine, bpa = 1,2-bi(4- pyridyl)ethane, and bpp = 1,3-bi(4-pyridyl)propane), have been prepared and characterized by elemental analysis, IR spectra, and X-ray diffraction. Complex 1 has a two-dimensional (2D) bilayer supramolecular network constructed from one-dimensional (1D) zigzag coordination chains via π 3 3 3 π interactions, whereas 2 exhibits a three-dimensional (3D) supramolecular network assembled from 1D coordination arrays through π 3 3 3 π interactions and weak C-H 3 3 3 O interactions. Complex 3 features a (4,5)-connected self-penetrating 3D coordination net with a (43 3 65 3 82)(43 3 62 3 8)(44 3 64 3 82)(45 3 65) topology. The 3D framework of 4 can be described as a trinodal (4,5)-connected (3 3 4 3 53 3 6)(3 3 52 3 62 3 84 3 9)(3 3 4 3 5 3 83) topology, which consists of 2D [Zn(nbta)] helical arrays and bpa pillars. Complex 5 has a 3D trinodal 4-connected (4 3 64 3 8)(44 3 62)(43 3 63) topology. Moreover, thermal stabilities and luminescent properties of complexes 1-5 have also been investigated.

Introduction Metal-organic coordination polymers have attracted considerable attention because of their potential applications as functional materials as well as their structural diversity and intriguing topologies.1-5 Ingenious designs of ligands (spacers) and the proper choice of metal ions (nodes) are the main keys to achieve the target coordination polymers. Among various organic ligands, polycarboxyl compounds have been extensively used as multifunctional tectons, due to their extension ability both in covalent bonding and supramolecular interactions (H-bonding and aromatic stacking).6,7 As a result, a great number of metal-polycarboxylate compounds displaying diverse frameworks from one-dimensional (1D) to three-dimensional (3D) have been designed and prepared so far.8 Compared with the widely used 1,3-benzenedicarboxylic acid, 1,3,5-benzenetricarboxylic acid, and 1,2,4,5-benzenetetracarboxylic acid, 1,2,3-benzenetricarboxylic acid has distinctive characteristics such as the lower molecular symmetry as well as the versatile coordination capability of forming both short bridges via the carboxylate groups and long bridges via the benzene ring. In this regard, 1,2,3-benzenetricarboxylic acid has been used to obtain some interesting coordination polymers.9 However, the coordination chemistry based on 5-nitro-1,2,3-benzenetricarboxylic acid, a derivative of 1,2,3benzenetricarboxylic acid, has rarely been studied.10 On the other hand, the employment of mixed ligands has been demonstrated to be a very effective approach for constructing diverse coordination frameworks.11,12 For example, the skillful introduction of 2,20 -bipyridyl-like chelating agents or 4,40 -bipyridyl-like bridging spacers as the auxiliary coligands into the metal-polycarboxylate assembled systems can form *To whom correspondence should be addressed. r 2010 American Chemical Society

attractive coordination architectures. In general, the 2,20 -bipyridyl-like ligands can act as the terminal ligands and provide potential sites for aromatic stacking interactions,13 whereas the 4,40 -bipyridyl-like building blocks may further extend the coordination arrays as reliable spacers.14 In our previous work, we have shown that the presence of the electron-donating (-CH3, -OCH3, and -C(CH3)3) noncoordinating groups in dicarboxylate ligands can generate coordination polymers that are completely different from those based on the parent dicarboxylate ligands.15 As part of our ongoing interests in exploring the influence of coexistent noncoordinated groups on the final structure of the metallosupramolecular assemblies, we chose 5-nitro-1,2,3benzenetricarboxylic acid with the electron-withdrawing group (-NO2) and diverse N-donor coligands (Scheme 1) to construct new coordination polymers. Herein, five different coordination polymers, {[Zn(Hnbta)(2,20 -bipy)] 3 H2O}n (1), {[Cd3(nbta)2(2,20 -bipy)2(H2O)2]}n (2), {[Cd3(nbta)2(bpa)2]}n (3), {[Zn2(nbta)(OH)(bpa)1.5] 3 2H2O}n (4), and {[Zn3(nbta)2(bpp)2(H2O)2]}n (5), will be presented. The thermal stabilities and luminescent properties of complexes 1-5 will also be discussed. Results and Discussion Structural Descriptions of 1-5. {[Zn(Hnbta)(2,20 -bipy)] 3 H2O}n (1). Singe-crystal X-ray diffraction reveals that the structure of 1 consists of a simple 1D ZnII-Hnbta chain, in which the ZnII ion is five-coordinated by three carboxylate-O atoms (Zn-O 1.965(1)-2.212(2) A˚) and two nitrogen atoms from the 2,20 -bipy ligand (Zn-N 2.053(2)-2.062(2) A˚), as shown in Figure 1a. Several parameters are often used to define the coordination geometry of penta-coordinated metal centers, and one of the most common is the τ factor Published on Web 04/28/2010

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Crystal Growth & Design, Vol. 10, No. 6, 2010

defined by Addison et al. (τ = 0 for a regular squarepyramidal geometry and τ = 1 for a regular trigonal-bipyramidal geometry).16 Here, the τ value is 0.11 for ZnII, which indicates a slightly distorted square-pyramid environment, in which O8A locates at the apical position and the basal plane consists of O2/O7A and N2/N3 atoms (in cis sites). The [Zn(2,20 -bipy)]2þ corners are joined by Hnbta spacers to afford a 1D zigzag chain with a period of 10.16 A˚, in which the two carboxylate groups of Hnbta show chelating and monodentate coordination modes (see Figure 1b). Crystal packing of 1 reveals that interchain π 3 3 3 π interaction exists (see Figure S1a, Supporting Information) between the 2,20 bipy ligands, with the centroid-centroid distances of 3.743 and 3.799 A˚. Such contacts link the 1D zigzag chains into a 2D bilayer structure (see Figure S1b, Supporting Information). Interestingly, voids of the 2D bilayer are filled by free water molecules with the presence of O-H 3 3 3 O interactions (O9 3 3 3 O1: 2.751, O9 3 3 3 O3: 2.638, and O9 3 3 3 O7: 2.977 A˚). {[Cd3(nbta)2(2,20 -bipy)2(H2O)2]}n (2). When Zn(II) is replaced by Cd(II), a 1D chain-like compound 2 is isolated. As illustrated in Figure 2a, the asymmetric unit of 2 consists of two crystallographically nonequivalent Cd(II) atoms (Cd1 and Cd2), both of which adopt the seriously distorted octahedral coordination geometry. Cd1 is surrounded by six O atoms from four nbta ligands (O2-O3-O3B-O5C at the basal plane and O5B-O2B at the axial positions), and Cd2 is ligated by three O atoms from two nbta ligands in trans positions and one water molecule as well as two nitrogen atoms from the 2,20 -bipy ligand (O2-O9-N2-N3 at the

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basal plane and O4B-O1 at the axial positions). The Cd-O distances range from 2.222(1) to 2.489(2) A˚, and the Cd-N distances are 2.324(2) and 2.363(2) A˚, respectively (see Table S1, Supporting Information). Because of the steric hindrance effect of 2,20 -bipy, 2 features a 1D chain-like structure with 2,20 -bipy dangling on two sides of it (see Figure 2b). Different from 1, the 2,20 -bipy ligands are parallel to the direction of the chain (see Figure S2a, Supporting Information), and thus, each chain is connected by four adjacent ones via π 3 3 3 π (centroid-centroid distance: 3.742 A˚) and C-H 3 3 3 O interactions (C16 3 3 3 O1: 3.061 A˚), forming a 3D supramolecular network (see Figure S2b, Supporting Information). {[Cd3(nbta)2(bpa)2]}n (3). Utilizing the bridging N,N0 -donor ligand bpa, instead of the chelating ligand 2,20 -bipy, three 3D complexes 3, 4, and 5 are obtained. Complex 3 crystallizes in space group P21/c and the asymmetry unit contains three crystallographically independent Cd centers. As shown in Figure 3a, Cd1 is coordinated by four nbta oxygen atoms and two trans bpp nitrogen atoms to give a CdO4N2 octahedral geometry, in which O2-O9-O11-O13 constitutes the equatorial plane and the apical positions are occupied by N4 and N6, whereas Cd2 and Cd3 adopt the distorted octahedral

Scheme 1

Figure 2. (a) Coordination environments of Cd in 2. Symmetry codes: A = -x þ 2, -y þ 1, -z þ 1; B = x, -y þ 1, z þ 1/2; C = -x þ 2, y, -z þ 3/2. (b) 1D chain of 2 viewed along the b axis.

Figure 1. (a) Coordination environment of Zn in 1. Symmetry code: A = x, -y þ 1, z - 1/2. (b) 1D zigzag chain of 1.

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Figure 3. (a) Coordination environments of Cd in 3. Symmetry codes: A = -x þ 2, y þ 1/2, -z þ 3/2; B = x, -y þ 1/2, z - 1/2; C = -x þ 1, -y þ 1, -z þ 1; D = -x þ 1, -y þ 1, -z þ 2; E = -x þ 2, -y þ 1, -z þ 1; F = -x þ 2, -y þ 1, -z þ 2. (b) 2D layer of 3. (c) 1D double-strand array of 3 along the c-axis. (d) Schematic representation of the (4,5)-connected (43 3 65 3 82)(43 3 62 3 8)(44 3 64 3 82)(45 3 65) topology in 3 (orange: Cd1; green: Cd2; purple: Cd3; blue: nbta). (e) Schematic view of the self-penetrating motif.

CdO5N geometry provided by five nbta oxygen atoms and one bpa nitrogen atom, in which O2-O2-O3D-O5D and O10-O12E-O6F-O1 compose the basal planes, and the axial positions are occupied by N5-O14C and O9-N3, respectively. The Cd-O/N bond distances are in the range of 2.1981(19)-2.500(2) A˚. The overall structure of 3 can be

described as a 3D framework consisting of Cd-nbta layers and bpa pillars. In the Cd-nbta layer, there are two types of nbta ligands: L1 (with N1) and L2 (with N2), both of which take the μ5-coordination mode. The 1,3-COO- of L1 and 1,2COO- of L2 alternately link the Cd3 centers to form 1D double-strand arrays (see Figure 3c), which are further bridged

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Figure 4. (a) Coordination environment of Zn in 4. Symmetry codes: A = -x þ 2, -y, -z þ 1; B = x - 1/2, -y þ 1/2, -z þ 1; C = x, -y, z þ 1/2; D = x þ 1/2, -y þ 1/2, -z þ 1. (b) and (c) 2D layer of 4. (d) Schematic representation of the trinodal (4,5)-connected net in 4 (orange: Zn1; green: Zn2; blue: nbta).

by the coordination interactions between Cd2/Cd3 and nbta to give a 2D Cd-nbta layer (see Figure 3b). To fully understand the structure of 3, the topological approach is applied to simplify such a 3D coordination network. Apparently, the nbta ligand takes the 5-connected mode (blue spheres in Figure 3d) to link five Cd ions, and Cd1/Cd3 also serve as

the 5-connected nodes (orange and purple spheres in Figure 3d), whereas each Cd2 ion is a 4-connected node (green spheres in Figure 3d). In this way, 3 can be reduced to a tetranodal (4,5)-connected framework with the (43 3 65 3 82)(43 3 62 3 8)(44 3 64 3 82)(45 3 65) topology (see Figure 3d). A careful inspection of this structure also suggests its self-penetrated

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Figure 5. (a) Coordination environments of Zn in 5. Symmetry code: A = x, -y þ 2, z þ 1/2; B = -x þ 3/2, y þ 1/2, -z þ 3/2; C = -x þ 1, y = -z þ 1/2; D = x, -y þ 2, z - 1/2; E = -x þ 1, -y þ 2, -z þ 1. (b) 1D chain of 5. (c) Schematic representation of the trinodal 4-connected (4 3 64 3 8)(44 3 62)(43 3 63) topology in 5 (orange: Zn1; green: Zn2; blue: nbta).

nature; that is, one 10-membered shortest circuit is penetrated by a rod of the same net (see Figure 3e). Although several (4,5)connected networks have been identified and categorized by O’Keeffe et al., such as bnn-a, ctn-x, ffa, ffb, gar-a, iac-a, ibd-a, mcf-d, nia-a, ocu-a, rtw, scu-f, sqp-a, tcs, and toc-a,17-19 to the best of our knowledge, complex 3 represents the first example of a self-penetrated coordination framework with tetranodal (4,5)-connected topology. {[Zn2(nbta)(OH)(bpa)1.5] 3 2H2O}n (4). Single-crystal X-ray diffraction reveals that complex 4 crystallizes in space group Pbcn with two crystallographically independent Zn ions. Zn1 is five-coordinated by one nitrogen atom from one bpa ligand, three carboxylate oxygen atoms from two nbta ligands, and one hydroxyl. The τ value here is of 0.85, indicating a distorted trigonal-bipyramid coordination environment (O9-N3-O4A at the basal plane and O1-O5A at the axial positions). Zn2 is six-coordinated by two nitrogen atoms of bpa in a trans fashion locating at the axial sites as well as three carboxylate oxygen atoms of nbta and one hydroxyl at the equatorial plane (see Figure 4a). The Zn-O and Zn-N bond distances are in the

range of 1.912(3)-2.307(3) and 2.071(4)-2.194(4) A˚, respectively. Similar to 3, the overall structure of 4 also can be described as a 3D framework with Zn-nbta layers and bpa spacers. Differently, in the Zn-nbta layer of 4 (see Figure 4b,c), the Zn2 ions are bridged by the nbta ligands to form [Zn(nbta)] 21 helical chains along [001] with a pitch of 18.543 A˚. The helical chains have opposite handedness and the adjacent chains are interconnected by the ZnO4 subunits. From the viewpoint of network topology, the 3D structure of 4 can be simplified to a trinodal (4,5)-connected (3 3 4 3 53 3 6)(3 3 52 3 62 3 84 3 9)(3 3 4 3 5 3 83) topology, in which Zn1 and nbta act as the 4-connected nodes (orange and blue spheres in Figure 4d), whereas Zn2 acts as the 5-connected node (green spheres in Figure 4d). The unit cell volume percent occupied by the cocrystallized water molecules is 8.8% as calculated by PLATON. Although pillared-layer structures have been well-known,14c such multinodal networks for 3 and 4 are rare. {[Zn3(nbta)2(bpp)2(H2O)2]}n (5). The asymmetric unit of 5 (see Figure 5a) consists of two crystallographically independent Zn(II) ions. Zn1 is surrounded by three O atoms from

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Ma et al. Scheme 2

two nbta ligands and one water molecule which form the equatorial plane as well as two trans nitrogen atoms from two bpp ligands at the apical positions. Zn2 is tetrahedrally coordinated by four oxygen atoms from four nbta ligands. The Zn-O lengths are in the range of 1.968(1)-2.251(1) A˚, and the Zn-N lengths are 2.097(2) and 2.139(2) A˚. The Zn1, Zn2, and Zn1A ions are bridged via carboxylate groups of two nbta ligands to form a trinuclear unit, in which the Zn1 3 3 3 Zn2 distance is 4.64 A˚. It is worth noting that the adjacent trinuclear subunits are bridged by paired nbta ligands to afford a 1D chain (see Figure 5b). These 1D chains are interconnected by the bpp spacers to form a 3D framework (see Figure 5c). From the topological view, Zn1 and Zn2 ions can be considered as two kinds of 4-connected nodes (orange and green spheres in Figure 5c), and the nbta ligands serve as 4-connected nodes (blue spheres in Figure 5c). As a result, the structure of 5 shows a trinodal 4-connected (4 3 64 3 8)(44 3 62)(43 3 63) topology (see Figure 5c). Structural Discussion. In complexes 1-5, the H3nbta ligand displays different degrees of deprotonation (Hnbta2for 1 and nbta3- for 2-5) and bridging fashions (see Scheme 2a for 1, 2b for 2, 2c and 2d for 3, 2e for 4, and 2c for 5). A comparison of the crystal structures of 1, 4, and 5 (ZnII complexes) as well as 2 and 3 (CdII complexes) clearly indicates that the auxiliary N-donor ligands have a significant influence on structural assembly of coordination architectures. When the terminal 2,20 -bipy ligand is introduced, the expected low-dimensional species 1 and 2 (1D) are obtained because the chelating ligand will inhibit the extension of the polymeric networks. However, when the auxiliary bridging ligands bpa and bpp are introduced into the systems, the resulting complexes 3-5 all show 3D coordination frameworks. On the other hand, the metal centers also play an important role in governing the coordination motifs and the final supramolecular structures. For instance, although complexes 1/2 and 3/4 were prepared by using Zn(OAc)2 3 2H2O and Cd(OAc)2 3 2H2O with the same organic ligands under similar hydrothermal conditions, they show completely different structures.

Figure 6. Solid-state emission spectra of 1 (black), 2 (red), 3 (green), 4 (blue), and 5 (cyan).

Until now, no H3nbta-ZnII or CdII complex incorporating 2,20 -bipy, bpa, or bpp coligand has been found by a Cambridge Structural Database (CSD) search,20 Hydrothermal reactions of Zn(II) or Cd(II) salt with bpe and H3nbta led to the formation of {[Cd3(nbta)2(bpe)2(H2O)2](H2O)2}n (6) and [Zn4(nbta)2(bpe)2(OH)2]n.(7).21 Both of which display unusual 3D self-penetrating coordination networks. Complex 6 displays the 4-connected frameworks with the Schl€ afli symbols of (4.62.72.8)2(42.62.7.8), and complex 7 shows a new 4-connected (42.63.8)4(64.8.10) topology, respectively. These results reveal that the auxiliary ligands make an important influence on the structural topologies of such complexes. In addition, the H3bta/4,40 -bipy/CdII and H3nbta/ZnII systems are available to make a structural comparison herein. In [Cd5(bta)2(Hbta)2(4,40 -bipy)3(H2O)2],9e the bta and Hbta ligands connect the CdII ions into a 2D layer along the ab plane, and the 4,40 -bipy pillars extend these layers into a 3D coordination framework. In {[Na2Zn5(μ3-OH)2(bta)4(H2O)4][Zn(H2O)6]}n 3 6nH2O,9a the bta ligands adopt two kinds of coordination modes to bridge the zinc(II) centers to form a 2D network with approximate ellipse-like channels.

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Table 1. Crystallographic Data for Complexes 1-5 compound

1

2

3

4

5

CCDC No. formula fw crystal system space group unit cell dimensions (A˚, °)

762840 C19H13N3O9Zn 492.69 monoclinic C2/c a = 26.386(2) b = 9.7824(9) c = 14.8774(14) β = 101.5410(10) 3762.5(6) 8 1.740 2000 1.001 R1 = 0.0276 wR2 = 0.0705

762841 C38H24Cd3N6O18 1189.83 monoclinic C2/c a = 14.5435(12) b = 23.860(2) c = 11.7516(10) β = 90.3700(10) 4077.7(6) 4 1.638 2328 1.072 R1 = 0.0168 wR2 = 0.0436

762842 C42H28Cd3N6O16 1209.90 triclinic P21/c a = 9.9286(8) b = 28.491(2) c = 14.9067(12) β = 93.6130(10) 4208.3(6) 4 1.585 2376 1.068 R1 = 0.0231 wR2 = 0.0537

762843 C27H25N4O11Zn2 712.25 orthorhombic Pbcn a = 18.543(3) b = 11.3866(16) c = 26.959(4) β = 90 5692.3(14) 8 1.662 2904 1.064 R1 = 0.0588 wR2 = 0.2256

762844 C44H36N6O18Zn3 1132.90 monoclinic C2/c a = 19.016(3) b = 23.278(3) c = 12.1307(18) β = 120.7780(10) 4613.4(12) 4 1.631 2304 1.037 R1 = 0.0228 wR2 = 0.0587

V (A˚3) Z F (g cm-3) F(000) GOF final R indices [I > 2σ(I)]

Thermal Analysis. Thermal stability of these new crystalline materials has been investigated by thermogravimetric (TG) analysis experiments of mass loss (see Figure S3, Supporting Information). The TG analyses of 1, 2, 4, and 5 show the first weight loss of 3.4% (calcd. 3.7%) for 1 (∼230 °C), 3.3% (calcd. 3.0%) for 2 (∼200 °C), 4.7% (calcd. 5.1%) for 4 (∼226 °C), and 3.6% (calcd. 3.2%) for 5 (∼220 °C), corresponding to the loss of coordinated or lattice water molecules per formula unit. After that, the weight loss occurs upon heating including three steps, which suggests the decomposition of the crystalline material. The final mass remnant is of 18.5% for 1, 29.8% for 2, 21.2% for 4, and 22.5% for 5 of the total sample. There is no mass loss for 3 until ca. 200 °C, whereupon expulsion of the organic components occurs and the final mass remnant at 800 °C is of 30.9% of the total sample. Luminescent Properties. To examine the luminescent properties of these d10 metal complexes, the luminescence spectra of 1-5 (see Figure 6) as well as of the free ligands H3nbta, 2,20 -bipy, bpa, and bpp (see Figure S4, Supporting Information) have been measured. Upon excitation at ca. 435 nm, complexes 1-5 exhibit intense fluorescence emission bands at ca. 533 nm for 1, 522 nm for 2, 545 nm for 3, 520 nm for 4 , and 530 nm for 5. These emissions are neither metal-toligand charge transfer (MLCT) nor ligand-to-metal transfer (LMCT) in nature, since ZnII and CdII ions are difficult to oxidize or reduce due to their d10 configuration.22 In comparison to that of the free H3nbta ligand, most of the emission maxima of complexes 1-5 are significantly shifted. The shifts of the emission bands are attributed to both the deprotonated effect of H3nbta and the coordination interactions of the organic ligands to ZnII and CdII ions.23 Conclusion II

II

Five Zn or Cd coordination polymers based on a novel polycarboxyl tecton H3nbta and different dipyridyl ligands have been prepared and characterized, which show diverse supramolecular architectures such as 2D bilayer network (1), 3D network (2), 3D self-penetrating architecture with the (43 3 65 3 82)(43 3 62 3 8)(44 3 64 3 82)(45 3 65) topology (3), 3D helical pillar-layer framework with the (3 3 4 3 53 3 6)(3 3 52 3 62 3 84 3 9)(3 3 4 3 5 3 83) topology (4) and 3D (4 3 64 3 8)(44 3 62)(43 3 63) network (5). The results demonstrate that the 5-nitro-1,2,3-benzenetricarboxylic acid ligand could be a potential building block to construct novel coordination polymers with interesting structures and physical properties. Subsequent works will be focused on syntheses, structures, and physical properties of

more coordination polymers with transition/rare metal ions and H3nbta or related derivatives. Experimental Section Materials and Physical Measurements. All reagents are of analytical grade. Elemental analyses for C, H, and N were performed on a Vario EL III elemental analyzer. Thermogravimetric analyses (TG) were carried out on a STA449C integration thermal analyzer. Infrared spectra (KBr pellet, 4000-600 cm-1) were recorded on an Avatar 360 E. S. P. IR spectrometer. Fluorescent spectra were recorded on a Hitachi F-4500 analyzer. Preparation of Complexes 1-5. {[Zn(Hnbta)(2,20 -bipy)] 3 H2O}n (1). A mixture of H3nbta (25.1 mg, 0.1 mmol), 2,20 -bipy (17.8 mg, 0.1 mmol), Zn(OAc)2 3 2H2O (22.0 mg, 0.1 mmol), KOH (5.6 mg, 0.10 mmol), and H2O (15 mL) was placed in a Teflon-lined stainless steel vessel, heated to 170 °C for 4 days, and then cooled to room temperature over 24 h. Colorless block crystals of 1 were obtained. Yield: 27.6 mg (56%, based on Zn). Elemental analysis (%): calcd for C19H13N3O9Zn: C 46.32, H 2.66, N 8.53; found: C 46.38, H 2.61, N 8.46. IR (cm-1): 3527m, 3396m, 1731s, 1602s, 1533m, 1432m, 1353s, 1261m, 824m, 771m. {[Cd3(nbta)2(2,20 -bipy)2(H2O)2]}n (2). Complex 2 was synthesized in a similar way as that for 1, except that Zn(OAc)2 3 2H2O was replaced by Cd(OAc)2 3 2H2O (26.7 mg, 0.1 mmol). Yield: 18.6 mg (47%, based on Cd). Elemental analysis (%): calcd for C38H24Cd3N6O18: C 38.36, H 2.03, N 7.06; found: C 38.45, H 2.08, N 7.01. IR (cm-1): 3376m, 3089m, 1601s, 1569s, 1558m, 1442m, 1245m, 1074m, 827m, 769m. {[Cd3(nbta)2(bpa)2]}n (3). A mixture of H3nbta (25.1 mg, 0.1 mmol), bpa (0.1 mmol, 18.4 mg), Cd(OAc)2 3 2H2O (26.7 mg, 0.1 mmol), KOH (0.1 mmol, 5.6 mg), and H2O (15 mL) was placed in a Teflon-lined stainless steel vessel, heated to 170 °C for 4 days, and then cooled to room temperature over 24 h. Colorless block crystals of 3 were obtained. Yield: 20.6 mg (51%, based on Cd). Elemental analysis (%): calcd for C42H28Cd3N6O16: C 41.69, H 2.33, N 6.95; found: C 41.60, H 2.30, N 6.88. IR (cm-1): 1674s, 1605m, 1557m, 1605m, 1557m, 1423m, 1347m, 1279m, 1073m, 1020m, 829m, 572m. {[Zn2(nbta)(OH)(bpa)1.5] 3 2H2O}n (4). Complex 4 was synthesized in a similar way as that for 1, except that 2,20 -bipy was replaced by bpa. Yield: 16.7 mg (47%, based on Zn). Elemental analysis (%): calcd for C27H25N4O11Zn2: C 45.59, H 3.54, N 7.88; found: C 45.63, H 3.48, N 7.80. IR (cm-1): 3619m, 3500m, 1664s, 1615s, 1579m, 1510m, 1420m, 1340m, 1066m, 1029m, 827m, 725m. {[Zn3(nbta)2(bpp)2(H2O)2]}n (5). Complex 5 was synthesized in a similar way as that for 1, except that 2,20 -bipy was replaced by bpp. Yield: 14.5 mg (38%, based on Zn). Elemental analysis (%): calcd for C44H36N6O18Zn3: C 46.65, H 3.20, N 7.42; found: C 46.58, H 3.15, N 7.32. IR (cm-1): 3563m, 3070m, 1619s, 1604s, 1578m, 1430m, 1339m, 1068m, 830m, 531m. X-ray Crystallography. Single crystal X-ray diffraction analyses of 1-5 were carried out on a Bruker SMART APEX II CCD diffractometer equipped with a graphite monochromated MoKR radiation (λ = 0.71073 A˚) by using φ/ω scan technique at room

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temperature. The structures were solved by direct methods with SHELXS-97. The H atoms were assigned with common isotropic displacement factors and included in the final refinement. A full-matrix least-squares refinement on F2 was carried out using SHELXL-97. The crystallographic data and selected bond geometries for 1-5 are listed in Tables 1 and S1 (Supporting Information).

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Acknowledgment. This work was financially supported by the National Natural Science Foundation of China (20771054), 2009GGJS-104 and the Foundation of Education Committee of Henan Province (2006150017 and 2008A150018). Supporting Information Available: Crystallographic data (CIF), selected bond parameters (Table S1) for 1-5, additional figures for 1 (Figure S1) and 2 (Figure S2), TGA curves for 1-5 (Figure S3), and solid-state emission spectra of the organic ligands (Figure S4). This material is available free of charge via the Internet at http:// pubs.acs.org. (9)

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