Supramolecular Coordination Complexes with 5-Sulfoisophthalic Acid

DOI: 10.1021/cg100144p

Supramolecular Coordination Complexes with 5-Sulfoisophthalic Acid and 2,5-Bipyridyl-1,3,4-Oxadiazole: Specific Sensitivity to Acidity for Cd(II) Species

2010, Vol. 10 2650–2660

Cheng-Peng Li, Qian Yu, Jing Chen, and Miao Du* 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 30, 2010; Revised Manuscript Received April 5, 2010

ABSTRACT: A series of CdII, CoII, NiII, and PbII mixed-ligand coordination complexes 1-8 based on 5-sulfoisophthalic acid (H3sip) and the bent dipyridyl ligand 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo) or its 4-pyridyl N-donor analogue (4-bpo) have been synthesized and fully characterized by IR spectra, microanalyses, and single crystal and powder X-ray diffraction techniques. The significant pH effect on assembly of the CdII complexes 1-4 has been demonstrated, which leads to the formation of distinct crystalline products, whereas the CoII, NiII, and PbII systems 5-8 are independent to pH condition of the synthetic reaction. Complexes 1-8 display various coordination motifs with different existing forms, conformations, and coordination modes of the organic ligands. Further, extended supramolecular networks are constructed via secondary interactions such as hydrogen-bonding and aromatic stacking. Solid-state properties of thermal stability and fluorescence for these crystalline materials are also presented.

Introduction The rational preparation of supramolecular coordination complexes is of great importance for developing new crystalline materials for their promising applications.1,2 Significant successes have been achieved in this regard, which are mainly based on a good understanding of the connection between the building blocks (organic or inorganic units) and the resulting lattice frameworks.3 However, owing to the fact that the assembly of such supramolecular systems may be easily affected by external physical or chemical stimuli, some typical factors, such as solvent,4 reaction temperature,5 and counterion,6 are normally critical in these processes. Generally speaking, the pH effect on constructing metal-organic architectures can be identified by its decisive domination of the existing forms and coordination fashions of organic ligands, the introduction of ancillary hydroxo bridges, crystallization kinetics, and so on.7a Especially for assembled systems involving polycarboxyl tectons, the pH parameter may sensitively determine the deprotonation degrees and charges of such ligands, which will affect their binding modes and the metal-to-ligand compositions in the products, and thus, the resulting coordination architectures. Moreover, since the carboxylate and carboxyl groups are always actively involved in H-bonding interactions, optimization of the pH condition may also be considered as a structure-directing factor from this viewpoint. In this context, the pH effect on structural assembly of some coordination systems has been well demonstrated.7-10 Recently, 5-sulfoisophthalic acid (H3sip) has inspired great research interest for assembling coordination architectures.11 As a versatile tecton, it contains two carboxylic and one sulfonic groups, which may be partially or completely deprotonated and normally serves as a trigonal-shaped connector to construct diverse metallosupramolecular systems via different *Corresponding author. E-mail: [email protected]. Tel./Fax: 86-2223766556. pubs.acs.org/crystal

Published on Web 04/20/2010

coordination and/or hydrogen-bonding modes. On the other hand, we have revealed that the bent dipyridyl ligands 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo) and its 4-pyridyl N-donor analogue (4-bpo) can be applied as nice candidates for coordination assemblies.12 Significantly, coordination systems with both 3-bpo/4-bpo and polycarboxyl are quite rare, although reliability of the mixed-ligand synthetic strategy has already been confirmed.12 Considering the aforementioned points, we have designed and synthesized a series of CdII, CoII, NiII, and PbII complexes based on H3sip and 3-bpo/4-bpo ligands under different pH conditions. Remarkably, the results indicate that the CdII complexes display the specific sensitivity to acidity of the reaction systems, leading to the formation of distinct crystalline products. Structural diversification of these supramolecular coordination complexes has been discussed and their related solid-state properties such as thermal stability and fluorescence have also been investigated. Experimental Section Materials and General Methods. With the exception of the ligands 3-bpo and 4-bpo that were synthesized according to the literature methods,13 all reagents and solvents were commercially available and used as received. Elemental analyses of C, H, and N were performed on a CE-440 (Leemanlabs) analyzer. Fourier transform (FT) IR spectra with KBr pellets were taken on an AVATAR-370 (Nicolet) spectrometer. Thermogravimetric analysis (TGA) experiments were carried out on a NETZSCH TG209 (Siemens) thermal analyzer in the temperature range of 25-650 °C at a heating rate of 10 °C/min under N2 atmosphere. Powder X-ray diffraction (PXRD) patterns were recorded on a Rigaku D/Max-2500 diffractometer at 40 kV and 100 mA for a Cu-target tube (λ = 1.5406 A˚), with a scan speed of 2°/min and a step size of 0.02° in 2θ. The calculated PXRD patterns were produced from the single-crystal diffraction data by using the PLATON software.14 Solid-state fluorescent spectra were measured on a Cary Eclipse spectrofluorimeter (Varian) at room temperature. The pH values of the solutions were determined by using a PP-15-P11 (Sartorius) acidity meter. r 2010 American Chemical Society

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

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Table 1. Crystal Data and Structural Refinement Summary for Complexes 1-8 chemical formula formula weight crystal size (mm) crystal system space group a (A˚) b (A˚) c (A˚) R (deg) β (deg) γ (deg) V (A˚3) Z Fcalcd (g cm-3) μ (mm-1) F(000) total/independent reflections parameters Rint Ra , Rw b GOFc

chemical formula formula weight crystal size (mm) crystal system space group a (A˚) b (A˚) c (A˚) R (deg) β (deg) γ (deg) V (A˚3) Z Fcalcd (g cm-3) μ (mm-1) F(000) total/independent reflections parameters Rint R a , Rw b GOFc

1

2

3

4

C40H43Cd3N8O26.5S2 1461.14 0.32 0.26 0.24 triclinic P1 8.1170(9) 10.098(1) 17.233(2) 85.000(1) 85.161(1) 70.801(1) 1326.6(2) 1 1.829 1.365 727 7259/4616

C20H18CdN4O11S 634.84 0.30 0.28 0.22 monoclinic P21/c 8.039(2) 30.041(8) 10.131(3) 90 109.934(4) 90 2300(1) 4 1.833 1.111 1272 11568/4060

C40H66Cd3N8O38S2 1668.33 0.28 0.16 0.14 monoclinic P21/c 7.0610(4) 20.683(1) 21.149(1) 90 96.811(1) 90 3066.8(3) 2 1.807 1.206 1684 16579/5407

C40H34CdN8O20S2 1123.27 0.22 0.20 0.16 triclinic P1 7.5981(5) 8.0697(5) 19.618(1) 83.022(1) 86.303(1) 67.154(1) 1100.1(1) 1 1.695 0.685 570 5691/3866

413 0.0183 0.0290, 0.0747 1.036

334 0.0333 0.0305, 0.0608 1.012

440 0.0143 0.0291, 0.0829 1.053

324 0.0140 0.0260, 0.0649 1.091

5

6

7

8

C68H68Co3N16O29S2 1814.29 0.34 0.15 0.14 monoclinic P21/c 13.5011(4) 13.9721(4) 21.2118(7) 90 94.339(1) 90 3989.9(2) 2 1.510 0.761 1866 19901/6994

C40H66Co3N8O38S2 1507.92 0.24 0.20 0.18 monoclinic P21/c 7.021(2) 20.296(7) 20.820(7) 90 97.699(6) 90 2940(2) 2 1.703 1.019 1558 14966/5188

C68H68Ni3N16O29S2 1813.63 0.24 0.18 0.16 monoclinic P21/c 13.503(3) 13.852(3) 21.216(4) 90 94.375(4) 90 3957(1) 2 1.522 0.852 1872 20152/6984

C80H78Pb4N16O47S4 2972.58 0.25 0.22 0.21 triclinic P1 11.4270(4) 14.3404(5) 15.1217(6) 89.392(1) 82.790(1) 84.044(1) 2445.1(2) 1 2.019 7.057 1438 12593/8581

546 0.0172 0.0349, 0.0962 1.096

412 0.0355 0.0364, 0.0799 1.005

549 0.0658 0.0512, 0.1187 1.106

715 0.0171 0.0236, 0.0555 1.071

)

)

R = Σ Fo| - |Fc /Σ|Fo|. bRw = [Σ[w(Fo2 - Fc2)2]/Σw(Fo2)2]1/2. c GOF = {Σ[w(Fo2 - Fc2)2]/(n - p)}1/2.

a

Preparation of the Complexes. {[Cd3(sip)2(3-bpo)2(H2O)6](H2O)4.5}n (1). To a hot methanol (10 mL) solution of 3-bpo (11.2 mg, 0.05 mmol) was added a water solution (10 mL) of H3sip (12.3 mg, 0.05 mmol) with stirring for 10 min. Then, a methanol (5 mL) solution of Cd(NO3)2 3 4H2O (15.4 mg, 0.05 mmol) was added to the above mixture with continuous stirring, the pH value of which was adjusted to ca. 2.5 by adding dropwise a water solution (0.1 M) of NaOH. The reaction solution was filtered after 30 min and left to stand at room temperature. Colorless block crystals of 1 were obtained by slow evaporation of the solvents after two weeks. Yield: 14.1 mg (58%, based on Cd(NO3)2 3 4H2O). Anal. Calcd for C40H43Cd3N8O26.5S2 (1): C, 32.88; H, 2.97; N, 7.67%. Found: C: 33.55; H, 3.32; N, 7.85%. IR (cm-1): 3437b, 1634s, 1559m, 1466w, 1439w, 1370s, 1201m, 1112m, 1047m, 926w, 876w, 780w, 727w, 691w, 627m. {[Cd(sip)(3-Hbpo)(H2O)](H2O)2}n (2). The same synthetic method as that for 1 was used except that the pH value of the reaction solution was adjusted to ca. 4.0, producing colorless block X-ray quality single crystals of 2 after one week in 62% yield (19.7 mg). Anal. Calcd for C20H18CdN4O11S (2): C, 37.84; H, 2.86; N, 8.83%. Found: 37.41; H, 2.52; N, 8.49%. IR (cm-1): 3420b, 3083m, 1609vs, 1552s, 1439m, 1373s, 1200s, 1104m, 1041m, 828w, 776w, 733m, 690w, 629m, 444w. {[Cd(sip)(4-bpo)(H2O)3]2[Cd(H2O)6](H2O)10}n (3). The same synthetic method as that for 1 was used except that 3-bpo was

replaced by 4-bpo (11.2 mg, 0.05 mmol). Colorless block crystals of 3 were obtained after one week in 40% yield (11.1 mg, based on Cd(NO3)2 3 4H2O). Anal. Calcd for C40H66Cd3N8O38S2 (3): C, 28.80; H, 3.99; N, 6.72%. Found: C, 28.36; H, 3.80; N, 6.39%. IR (cm-1): 3435b, 1615s, 1562s, 1428m, 1371s, 1210m, 1111w, 1049m, 836w, 780w, 722w, 626w, 451w. [Cd(H2sip)2(4-bpo)2(H2O)2](H2O)2 (4). The same synthetic method as that for 1 was used except that 3-bpo was replaced by 4-bpo (11.2 mg, 0.05 mmol) and the pH value of the reaction solution was adjusted to ca. 4.0. Colorless block crystals of 4 were produced after five days in 61% yield (17.1 mg, based on H3sip). Anal. Calcd for C40H34CdN8O20S2 (4): C, 42.77; H, 3.05; N, 9.98%. Found: C, 42.52; H, 3.46; N, 10.26%. IR (cm-1): 3476b, 1728s, 1621s, 1489w, 1422s, 1381m, 1256m, 1175m, 1110m, 1043m, 842w, 780w, 721w, 620s, 481m. [Co(sip)(3-bpo)(CH3OH)(H2O)]2[Co(3-bpo)2(H2O)4](CH3OH)2(H2O) (5). The same synthetic method as that for 1 was used except that Cd(NO3)2 3 4H2O was replaced by Co(OAc)2 3 4H2O (12.6 mg, 0.05 mmol). Red block crystals of 5 were obtained after two days in 56% yield (12.6 mg, based on 3-bpo). Anal. Calcd for C68H68Co3N16O29S2 (5): C, 45.02; H, 3.78; N, 12.35%. Found: C, 44.74; H, 3.3.92; N, 11.89%. IR (cm-1): 3392b, 1609vs, 1554vs, 1485w, 1421s, 1368s, 1194s, 1101m, 1042m, 782w, 699s, 624m, 454w.

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Li et al. Scheme 1

{[Co(sip)(4-bpo)(H2O)3]2[Co(H2O)6](H2O)10}n (6). The same synthetic procedure as that for 1 was used except that 3-bpo and Cd(NO3)2 3 4H2O were replaced by 4-bpo (11.2 mg, 0.05 mmol) and Co(OAc)2 3 4H2O (12.6 mg, 0.05 mmol), respectively. Red block crystals of 6 were produced after one week in 42% yield (10.6 mg, based on Co(OAc)2 3 4H2O). Anal. Calcd for C40H66Co3N8O38S2 (6): C, 31.86; H, 4.41; N, 7.43%. Found: C, 31.55; H, 4.02; N, 6.95%. IR (cm-1): 3446b, 1611s, 1553s, 1426m, 1361vs, 1188s, 1104w, 1044m, 845w, 781w, 714m, 627m, 571w, 526w, 455w. [Ni(sip)(3-bpo)(CH3OH)(H2O)]2[Ni(3-bpo)2(H2O)4](CH3OH)2(H2O) (7). The same synthetic method as that for 1 was used except that Cd(NO3)2 3 4H2O was replaced by Ni(OAc)2 3 4H2O (12.5 mg, 0.05 mmol). Green block crystals of 7 were obtained after two days in 36% yield (8.2 mg, based on 3-bpo). Anal. Calcd for C68H68Ni3N16O29S2 (7): C, 45.04; H, 3.78; N, 12.36%. Found: C, 45.26; H, 3.44; N, 12.73%. IR (cm-1): 3400b, 1611vs, 1553vs, 1486w, 1423s, 1369s, 1211s, 1173s, 1103m, 1038s, 825w, 781w, 700m, 624m, 455w. [Pb2(Hsip)2(4-bpo)2(H2O)2]2(H2O)11 (8). The same synthetic procedure as that for 1 was used except that 3-bpo and Cd(NO3)2 3 4H2O were replaced by 4-bpo (11.2 mg, 0.05 mmol) and Pb(NO3)2 3 H2O (17.6 mg, 0.05 mmol), respectively. Pale yellow block crystals of 8 were obtained after one week in 51% yield (19.0 mg). Anal. Calcd for C80H78Pb4N16O47S4 (8): C, 32.32; H, 2.64; N, 7.54%. Found: C, 31.95; H, 2.27; N, 7.19%. IR (cm-1): 3409b, 3086m, 1712s, 1633s, 1571w, 1530w, 1488m, 1419s, 1178vs, 1101m, 1039s, 852s, 750w, 677w, 619m, 497w. X-ray Crystallography. Single-crystal X-ray diffraction data for complexes 1-8 (CCDC reference numbers: 761733-761740) were collected on a Bruker Apex II CCD diffractometer with Mo KR radiation (λ = 0.71073 A˚) at room temperature. There was no evidence of crystal decay during data collection. In each case, a semiempirical absorption correction was applied (SADABS) and the program SAINT was used for integration of the diffraction profiles.15 All structures were solved by direct methods using SHELXS and refined with SHELXL.16 The final refinements were finished by full-matrix least-squares methods with anisotropic thermal parameters for all non-H atoms on F2. Generally, C-bound hydrogen atoms were placed geometrically and refined as riding, whereas O- and N-bound H atoms were first determined in difference Fourier maps and then fixed in the calculated positions. Isotropic displacement parameters of the H atoms were derived from their parent atoms. Notably, the lattice water molecules of O13 (in 1) and O15 (in 5 and 7) are disordered over three and two positions, respectively, with the site occupancy factors of 0.40/0.40/ 0.20 and 0.25/0.25. In addition, the lattice water molecules of O14 (in 1) and O24 (in 8) were assigned to 1/4 and 1/2 occupancy, respectively, to obtain the appropriate thermal parameters. Thus, the affiliated H atoms for these water molecules were not determined. Furthermore, the sip3- ligands in 1 and 3, and one sip3- in 8 were treated by using a disorder model with each sulfonate group

adopting two different locations. Further crystallographic details are summarized in Table 1. Selected bond parameters and important hydrogen-bonding geometries are listed in Table S1 and Table S2 (see Supporting Information).

Results and Discussion Synthesis and General Characterization. Complexes 1-8 were similarly synthesized by direct solution assemblies of the equimolar metal/bpo/H3sip mixture under ambient conditions. In each case, the crystalline product was characterized by IR spectrum, microanalysis, and single crystal X-ray diffraction, and phase purity of the bulk sample was confirmed by the PXRD technique (see Figure S1, Supporting Information). Significantly, the pH value of the reaction solution is critical to form different products for the CdII complexes 1-4, which however, is not the case for other systems such as CoII, NiII, and PbII (see Scheme 1). That is, complexes 5-8 can be uniformly obtained in a wide pH range of 2.5-7.0, and in contrast, assemblies of the CdII complexes seem sensitive to the pH values of the reaction systems. In a typical case as given in the Experimental Section, the pH values of the reaction solutions before/after crystallization are ca. 2.5/1.5 for 1, 4.0/2.6 for 2, 2.5/1.5 for 3, and 4.0/3.9 for 4, respectively. Further experiments indicate that complexes 2 and 4 can be readily produced in the pH range of 4.0-7.0, and when the pH value is lower than 2.0, no crystalline product is observed after the solution is dried up by evaporation. In addition, the mother liquor of 2 after crystallization and the starting reaction solution of 1 have similar pH values (2.6 vs 2.5) and equivalent stoichiometric ratios of the reagents. However, no crystalline product of 1 can be obtained from the mother liquor of 2 until a complete solvent evaporation. In this regard, it should be noted that the concentration for each reaction component in the mother liquor will be changed after evaporation of the solvents and precipitation of 2, which may also affect the crystallizing process. In the IR spectra of 1-8, the broad peaks centered at ca. 3400 cm-1 indicate the O-H characteristic stretching vibrations of water, methanol, and/or carboxyl. In the IR spectra of 1-3 and 5-7, the absence of characteristic absorption band of carboxyl (ca. 1700 cm-1) confirms a complete deprotonation of H3sip. As a consequence, the

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Figure 1. Crystal structure of 1. (a) Coordination geometries of CdII (symmetry codes for A = -x þ 3, -y, -z þ 1; B = x, y - 1, z; C = -x þ 1, -y þ 2, -z þ 2). (b) 1-D coordination array consisting of Cd2 ions and sip3-. (c) 2-D coordination layer (the backbones of sip3- are reduced to gray rods for clarity). (d) 3-D net showing interlayer H-bonding interactions (the water ligands around Cd1 are omitted for clarity).

antisymmetric and symmetric stretching vibrations of carboxylate appear in 1609-1634 and 1361-1373 cm-1, respectively. The IR spectra of 4 and 8 display strong absorption peaks at 1728 and 1712 cm-1, respectively, indicating the presence of carboxyl groups coming from H2sip- and Hsip2- anions. Structural Description of 1-8. {[Cd3(sip)2(3-bpo)2(H2O)6](H2O)4.5}n (1) and {[Cd(sip)(3-Hbpo)(H2O)](H2O)2}n (2). Complexes 1 and 2 can be regarded as the result of pH-directed assemblies. The asymmetric unit of 1 consists of one and a half CdII ions, one sip3- anion, one 3-bpo ligand, three water ligands, and two and quarter lattice water molecules. As shown in Figure 1a, Cd1 is located at an inversion center and ligated by four O atoms of water and two pyridyl N atoms of 3-bpo to afford a nearly ideal octahedral geometry, while the distorted pentagonal-bipyramidal geometry of Cd2 is provided by five carboxylate O atoms from three sip3-, one water ligand, and one pyridyl N atom from 3-bpo. In this structure, the carboxy-


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late groups of sip3- behave as the η-O,O0 and μ-O,O-η-O,O0 coordination modes, connecting the Cd2 ions to result in a 1-D coordination motif along [010] with the dimeric [Cd2O2] units, in which the Cd 3 3 3 Cd separation is 3.683(1) A˚ (see Figure 1b). Such 1-D [(Cd2)(sip)]n arrays and Cd1 centers are further extended by trans-3-bpo spacers to afford a 2-D polymeric layer (see Figure 1c), in which the Cd1 3 3 3 Cd2 distance separated by 3-bpo is 12.507(1) A˚. Interestingly, the water ligand (O11) of each layer is hydrogen bonded (O11-H11B 3 3 3 O3) to the carboxylate group of an adjacent layer, leading to the formation of a 3-D supramolecular network (see Figure 1d), which is also consolidated by H-bonding involving coordinated water, sulfonate, and pyridyl (O9-H9B 3 3 3 O7, O10H10A 3 3 3 O6, and O10-H10B 3 3 3 N2). And as well, the lattice water guests (O11 and O12) located in the 3-D framework are involved in the host-guest (O12-H12A 3 3 3 O4 and O12H12B 3 3 3 O8) and guest-guest (O11-H11A 3 3 3 O12) H-bonding interactions. In the structure of complex 2, the asymmetric unit is composed of one CdII ion, one sip3- anion, one protonated 3-Hbpo in trans-conformation, one water ligand, and two lattice water molecules. The distorted pentagonalbipyramidal sphere of CdII (see Figure 2a) is defined by a pair of chelated carboxylate groups and one terminal pyridyl from 3-Hbpo in the equatorial plane, as well as one carboxylate and one aqua ligand at the axial sites. For 5-sulfoisophthalic acid, it is completely deprotonated and coordinates to CdII via two carboxylate groups in η-O,O0 and μ-O, O-η-O,O0 modes, respectively. As a result, the sip3- anionic components interlink the CdII centers to result in a 1-D coordination motif along [001], which is similar to that in 1. However, one pyridyl group of 3-bpo in this case is protonated, and as a result, the 3-bpo ligands act as the terminal pendants to decorate the 1-D array along two sides (see Figure 2b). Notably, each water ligand is H-bonded to one carboxylate of sip3-, and such interchain O8-H8A 3 3 3 O3 interactions extend the 1-D motifs into a 2-D layered network (see Figure 2c). Further, such layers showing a parallel arrangement are connected by interlayer N4-H4A 3 3 3 O6 H-bonds between protonated pyridyl rings and sulfonate groups, forming a 3-D supramolecular network (see Figure 2d). Multiform H-bonds also exist between lattice water and protonated pyridyl/coordinated water/ sulfonate/carboxylate (N4-H4A 3 3 3 O11, O8-H8B 3 3 3 O10, O10-H10A 3 3 3 O7, O11-H11A 3 3 3 O7, O11-H11B 3 3 3 O5, and O10-H10B 3 3 3 O2). {[Cd(sip)(4-bpo)(H2O)3]2[Cd(H2O)6](H2O)10}n (3) and [Cd(H2sip)2(4-bpo)2(H2O)2](H2O)2 (4). Assemblies of CdII, 4-bpo, and H3sip at different pH values also result in two distinct crystalline products 3 and 4. The structure of 3 contains two types of coordination motifs, including the [Cd(sip)(4-bpo)(H2O)3]n anionic chain and the centrosymmetric [Cd(H2O)6]2þ cation. As depicted in Figure 3a, the Cd1 ion takes a distorted octahedral geometry via coordinating to two pyridyl nitrogen atoms of 4-bpo and four oxygen atoms of one sip3- plus three aqua ligands, whereas the octahedral Cd2 center is provided by six aqua molecules. The adjacent Cd1 centers are linked by the 4-bpo spacers to form a 1-D zigzag array along [010], with the [Cd(H2O)6]2þ units locating in its lateral voids (see Figure 3b). Intrachain O11-H11B 3 3 3 O3 as well as interchain O9-H9A 3 3 3 O7, O9-H9B 3 3 3 O4, O11-H11A 3 3 3 O5, O10-H10B 3 3 3 N2, and O10-H10B 3 3 3 N3 bonds between coordinated water and carboxylate/sulfonate/oxadiazole are found to assemble

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Li et al.

Figure 2. Crystal structure of 2. (a) Coordination environment of CdII (symmetry codes for A = x, y, z - 1; B = -x þ 1, -y, -z þ 2). (b) 1-D coordination motif. (c) 2-D Cd-sip3- layer constructed by interchain O-H 3 3 3 O bonds. (d) 3-D network via N-H 3 3 3 O bonding between the 2-D layers.

these 1-D motifs into a 2-D layer along the bc plane (see Figure 3c). Additionally, two types of intralayer aromatic stacking interactions are observed between oxadiazole and pyridyl as well as between a pair of pyridyl rings of 4-bpo. Their respective centroid-to-centroid distances are 3.775(2) and 3.827(2) A˚ and the dihedral angles are 1.8 and 4.0°. Moreover, the O10-H10A 3 3 3 O5 bonds interlink the adjacent layers to form a 3-D supramolecular framework, in which the [Cd(H2O)6]2þ entities and lattice water molecules are located in the intralayer and interlayer regions (see Figure 3, panels d and e), respectively, with the presence of multiple H-bonding interactions (see Table S2, Supporting Information for details). Each half-occupied CdII ion in the mononuclear complex 4, lying on a symmetric center, is six-coordinated by two

pyridyl nitrogen atoms from 4-bpo as well as four oxygen atoms from two water ligands and two sulfonate groups to constitute an octahedral sphere (see Figure 4a). Notably, only the sulfonate is deprotonated in the H2sip- ligand, facilitating the formation of O5-H5 3 3 3 O7 and O8H8B 3 3 3 O2 hydrogen bonds between two carboxyl groups as well as between water ligand and sulfonate. And thus, a 2-D supramolecular layer is constructed along the ab plane (see Figure 4b). Moreover, one carboxyl group of H2sip- is also H-bonded to the uncoordinated pyridyl ring of 4-bpo, and such O6-H6 3 3 3 N4 interactions link the 2-D layers into a 3-D network (see Figure 4c). In addition, each lattice water molecule plays a trifurcate role, serving as both H-bonding donor (O10-H10A 3 3 3 O3/O10-H10B 3 3 3 O1) and acceptor (O8-H8A 3 3 3 O10). Furthermore, several types of aromatic

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Figure 3. Crystal structure of 3. (a) Coordination geometries of CdII (symmetry codes for A = -x þ 1, y þ 1/2, -z þ 1/2; B = -x, -y þ 2, -z). (b) 1-D zigzag chain with [Cd(H2O)6]2þ ions locating in the lateral space. (c) 2-D layered network showing intra/interchain O-H 3 3 3 O interactions (the 4-bpo ligands are reduced to rods for clarity). (d) 3-D net with the inclusion of [Cd(H2O)6]2þ (the 4-bpo ligands are reduced to rods for clarity). (e) Schematic illustration showing the distribution of [Cd(H2O)6]2þ cations and lattice water molecules in the 3-D architecture.

stacking interactions are observed involving oxadiazole, pyridyl, and phenyl groups, with their centroid-to-centroid distances and dihedral angles in the range of 3.632(1)-3.879(2) A˚ and 0-4.0°, respectively. [Co(sip)(3-bpo)(CH 3 OH)(H 2 O)]2 [Co(3-bpo)2 (H 2 O)4 ](CH3OH)2(H2O) (5). Two different coordination patterns are found in 5, including a dinuclear entity [Co2(sip)2(3-bpo)2(CH3OH)2(H2O)2] and a mononuclear motif [Co(3-bpo)2(H2O)4] (see Figure 5a). In this case, each Co1 ion is six-coordinated by two pyridyl nitrogen atoms of 3-bpo and

four oxygen atoms coming from two carboxylates of sip3-, one methanol, and one water. For Co2, the octahedral coordination geometry is provided by two pyridyl nitrogen donors of 3-bpo and four water ligands. Both the bridging and terminal 3-bpo ligands in the dinuclear and mononuclear units, respectively, display the cis-conformation. Hydrogen bonds of O10-H100 3 3 3 O4 and O11-H11B 3 3 3 O6 are found within the dinuclear patterns, which are further extended into a 2-D layer along the bc plane via O11H11A 3 3 3 O9 interactions between water and sulfonate

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Figure 4. Crystal structure of 4. (a) Coordination environment of CdII (symmetry code for A = -x þ 1, -y þ 1, -z þ 1). (b) 2-D Cd-H2sip- layer constructed by intermolecular O-H 3 3 3 O bonds. (c) 3-D network generated by O-H 3 3 3 O and O-H 3 3 3 N hydrogen bonds.

(see Figure 5b). Moreover, the [Co(3-bpo)2(H2O)4] units are located in the interlayer interspaces with the presence of aromatic stacking between their parallel and adjacent oxadiazole groups of 3-bpo (centroid-to-centroid distance: 3.307(2) A˚), which are also interacted with the neighboring layers via H-bonding (O12-H12A 3 3 3 O7, O13-H13A 3 3 3 O8, and O13-H13B 3 3 3 N2) to afford a 3-D supramolecular network (see Figure 5, panels c and d). Additionally, secondary interactions exist such as O12-H12B 3 3 3 O14 between the 3-D network and lattice methanol as well as O15 3 3 3 O14 (2.913 A˚) between lattice water and methanol. {[Co(sip)(4-bpo)(H2O)3]2[Co(H2O)6](H2O)10}n (6) and [Ni(sip)(3-bpo)(CH3OH)(H2O)]2[Ni(3-bpo)2(H2O)4](CH3OH)2(H2O) (7). Complexes 6 and 7 are isostructural to complexes 3 and 5, respectively, and thus, their crystal structures will not be described in detail herein.

Li et al.

[Pb2(Hsip)2(4-bpo)2(H2O)2]2(H2O)11 (8). Lead(II) ion, due to its large radius and 6s2 outer electron,17 may adopt adaptable geometries to construct unusual coordination architectures.18 Complex 8 shows a tetranuclear motif, in which the crystallographically independent Pb1 and Pb2 ions take different coordination spheres (see Figure 6a). Pb1 is primarily coordinated by one nitrogen atom from 4-bpo, and four oxygen atoms from two carboxylate groups of Hsip2and one water ligand, showing a distorted square-pyramidal sphere (τ = 0.33).19 Pb2 exhibits a distorted octahedral geometry defined by one nitrogen donor of 4-bpo, and five oxygen atoms of two carboxylates, one sulfonate, and one water molecule. The carboxylate groups of both Hsip2ligands show the η-O,O0 -μ-O,O coordination mode, whereas the sulfonate groups thereof are unidentate and uncoordinated, respectively. The resulting tetranuclear motifs are further extended by O6-H6 3 3 3 N8 and O12-H12A 3 3 3 N4 H-bonds between carboxyl and uncoordinated 4-pyridyl groups to afford a 2-D network (see Figure 6b). Such 2-D layers are arranged in a parallel mode and connected via interlayer O17-H17B 3 3 3 N6 interactions to generate a 3-D supramolecular framework (see Figure 6c). Notably, the lattice water molecules are found to interact with this host net via multiple O-H 3 3 3 O bonding (see Table S2, Supporting Information for details), which will stabilize the overall 3-D crystalline lattice. Aromatic stacking interactions involving oxadiazole, pyridyl, and phenyl rings are also observed, with their centroid-to-centroid distances and dihedral angles of 3.538(2)-3.714(2) A˚ and 2.5-5.9°, respectively. Effect of pH Condition and Metal Ion on Assembly. This work is aiming to illustrate the influence of acidity for reaction solutions on forming the coordination complexes with H3sip, bpo, and different metal ions (see Scheme 1). As for the CdII complexes 1-4, the pH values of the reaction solutions play a key role in determining the final products; that is, coordination polymers 1 (2-D layer) and 3 (1-D zigzag chain) are obtained at a lower pH value (ca. 2.5), whereas complexes 2 (1-D tape) and 4 (mononuclear) can be isolated at a higher pH region (ca. 4.0-7.0). On the other hand, the pH values of the reaction solutions will be significantly decreased after crystallization of complexes 1-3 (ΔpH ≈ 1 for 1/3 and 1.4 for 2), whereas for 4, it is almost unchanged. A possible explanation for this observation is that the isolation of complexes 1-3 incorporating the sip3component will increase the concentration of hydrion in the mother liquors due to the complete deprotonation of H3sip, whereas for 4, this effect is inapparent as the monodeprotonated H2sip- is included in the final product. Moreover, with regard to other metal ions (CoII, NiII, and PbII), such a pH effect on assembly is not valid, indicating its specific selectivity to CdII. From a molecular level, the structural discrepancy for these complexes will be assigned to the different coordination fashions and conformations of the organic ligands (see Scheme 2), which in fact, are also dependent on the metal centers. For instance, the sip3- anions in 1 and 2 have the same binding mode (see Scheme 2a), whereas the 3-bpo ligands are trans-bridging in 1, and protonated and unidentate in 2, resulting in different structural patterns. On the other hand, in the isostructural CoII and NiII complexes 5 and 7, both bridging and terminal cis-3-bpo ligands are observed and the sip3- anions are coordinated to the metal centers via two unidentate carboxylate groups (see Scheme 2d), leading to the formation of a completely different

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Figure 5. Crystal structure of 5. (a) Coexisting dinuclear and mononuclear coordination units (symmetry codes for A = -x þ 1, -y, -z; B = -x, -y þ 1, -z þ 2). (b) 2-D H-bonding layer constructed by O-H 3 3 3 O interactions between the dinuclear units (the 3-bpo ligands are reduced to rods for clarity). (c) 3-D network showing the H-bonding interactions between one [Co(3-bpo)2(H2O)4]2þ unit (only the coordinated pyridyl nitrogen atoms of the unidentate 3-bpo ligands are shown) and the adjacent layers (the 3-bpo ligands are reduced to rods for clarity). (d) Schematic illustration showing the distribution of lattice water/methanol molecules in the 3-D architecture.

coordination architecture in comparison to those of 1 and 2. For complexes 3 and 4, the 4-bpo ligands take the bridging and terminal coordination modes, respectively, and the binding fashions of sip3- (for 3, see Scheme 2b) and H2sip-

(for 4, see Scheme 2c) are also different. Notably, in the PbII complex 8, there are two types of Hsip2- anions (see Scheme 2, panels e and f ), in one of which the sulfonate group is involved in metal coordination that is also observed in 4.

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Li et al. Scheme 2

Figure 6. Crystal structure of 8. (a) Tetranuclear coordination motif (symmetry code for A = -x þ 2, -y, -z þ 1). (b) 2-D Hbonding layer constructed by intermolecular O-H 3 3 3 N interactions between the tetranuclear units. (c) 3-D network generated by interlayer O-H 3 3 3 N interactions.

Thermal Stability. All complexes are air stable and their thermal stabilities were studied by TGA experiments (see Figure S2, Supporting Information). The TGA curve of 1 shows the first weight loss of 5.1% in the region of 40-112 °C, corresponding to the elimination of lattice water molecules (calculated: 5.5%). The residual solid starts to decompose at 266 °C with a series of consecutive weight losses that do not stop until the heating end. The final residual species holds a weight of 33.9% of the total sample, and seems to be cadmium carbonate (calculated: 35.4%). For 2, the first weight loss of 5.6% in 47-122 °C indicates the exclusion of lattice water molecules (calculated: 5.7%). Pyrolysis of the residue occurs at 213 °C with a sharp weight loss stopping at 293 °C, and further heating to 650 °C results in a complete weight loss of the sample due to the sublimation of cadmium sulfide in N2. The TGA curves of 3 and 6 are

similar for their isostructural nature. The first weight loss of 17.2% (50-168 °C) for 3 and 17.1% (56-217 °C) for 6 indicates the exclusion of 10 lattice and 6 coordinated water molecules (calculated: 17.3% and 19.1%). Pyrolysis of the residual components for 3 and 6 starts at 349 and 359 °C, respectively, which does not stop until the heating end. The final residues (34.3% for 3 and 33.8% for 6) cannot be specifically identified and may be a mixture. Complex 4 suffers a series of weight losses from 30 to 635 °C and the final residue has a weight of 17.2% of the total sample, corresponding to that of cadmium sulfite (calculated: 17.1%). The isostructural complexes 5 and 7 also display similar thermal behaviors, showing a series of continuous weight losses from 30 to 650 °C. The residual solids have the weights of 22.4% and 23.7% of the original samples for 5 and 7, respectively, which can be properly assigned to cobalt sulfite (calculated: 23.0%) and nickel sulfite (calculated: 23.0%). For 8, the first weight loss of 6.2% (calculated: 6.7%) in the range of 38-109 °C reveals the exclusion of lattice water molecules. With that, the remaining solid is thermally stable to 358 °C, and then shows a series of weight losses that do not stop until the heating end. The final product holds a weight of 23.6% of the total sample and seems to be a mixture. Photoluminescence Properties. Coordination complexes constructed from d10 metal centers and conjugated organic ligands are promising candidates for photoactive crystalline materials with potential applications.20 Thus, solid-state fluorescent spectra of complexes 1-4 (CdII) and 8 (PbII) were recorded at room temperature, which show the maximum emission bands at 362 (λex =320 nm), 390 (λex =340 nm), 366 (λex =320 nm), 378 (λex =320 nm), and 380 (λex = 340 nm) nm, respectively (see Figure 7). Moreover, the maximal emissions of 3-bpo and 4-bpo ligands are observed at 393 and 417 nm (λex =345 and 370 nm). Accordingly, the emission peaks of these coordination complexes should be ascribed to intraligand π f π* and/or n f π* transitions of either 3-bpo or 4-bpo, and their significant blue-shift (except for 2 that shows a slight blue-shift) compared with that of the corresponding free 3-bpo or 4-bpo ligand may be caused by the metal-ligand coordination interactions. In addition, the fluorescent intensity of 8 is evidently weaker than those of

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Supporting Information Available: Crystallographic data in CIF format, tables for selected bond parameters and important hydrogen-bonding geometries, powder X-ray diffraction (PXRD) patterns, and thermogravimetric analysis (TGA) curves for 1-8. This material is available free of charge via the Internet at http://pubs. acs.org.

References

Figure 7. (a, b) Solid-state fluorescent emission spectra.

4-bpo and the analogous CdII complexes 3 and 4, which may be ascribed to the heavy atom effect of PbII. Conclusions and Perspective Eight new supramolecular complexes based on different MII ions (CdII, CoII, NiII, and PbII), 5-sulfoisophthalic acid, and two isomeric bent dipyridyl ligands, have been presented, which show diverse coordination motifs (0D, 1-D, and 2-D) and extended network architectures via further H-bonding and aromatic stacking interactions. Their structural diversification should originate from the intrinsic difference of metal ions as well as the organic ligands with adaptable existing forms, coordination fashions, and conformations. Of further importance, the CdII systems are observed to show the specific sensitivity to the pH condition of reaction medium, which however is not valid for other metal-directed assemblies. This interesting observation prompts us to further develop the rational synthetic strategy to obtain new crystalline materials via an appropriate external stimulus. Acknowledgment. This work was financially supported by the National Natural Science Foundation of China (20671071 and 20971098), Program for New Century Excellent Talents in University (NCET-07-0613), Tianjin Normal University (52X09004), and SRF for ROCS, SEM.

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Supramolecular Coordination Complexes with 5-Sulfoisophthalic Acid

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