Five d10 3D Metal−Organic Frameworks Constructed From Aromatic

(a) Bayon , J. C.; Gemma , N. P. G.; Kolowich , R. B. J. Chem. Soc., Dalton Trans. 1987, 3003. [Crossref], [CAS]. 8. Dinuclear rhodium and iridium com...
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CRYSTAL GROWTH & DESIGN

Five d10 3D Metal-Organic Frameworks Constructed From Aromatic Polycarboxylate Acids and Flexible Imidazole-Based Ligands

2008 VOL. 8, NO. 9 3345–3353

Jian-Di Lin,†,‡ Jian-Wen Cheng,†,‡ and Shao-Wu Du*,† State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China, and Graduate UniVersity of Chinese Academy of Sciences, Beijing 100039, P. R. China ReceiVed March 11, 2008; ReVised Manuscript ReceiVed May 14, 2008

ABSTRACT: Five new metal-organic frameworks, namely, [Cd(HIDC)(bix)]n (1), [Cd2(BDC)2(mbix)H2O]n (2), [Cd(HBTEC)(H2bix)0.5]n (3), [Cd(BTEC)(H2mbix)]n (4), and [Zn(BTEC)0.5(mbix)]n (5) (H3IDC ) imidazole 4,5-dicarboxylic acid, H2BDC ) 1,4-benzenedicarboxylate, H4BTEC ) 1,2,4,5-benzenetetracarboxylate, bix ) 1,4-bis(imidazol-1-ylmethyl)-benzene, and mbix ) 1,3-bis(imidazol-1-ylmethyl)-benzene), have been synthesized under hydrothermal conditions by employing mixed ligands of various carboxylic acids with bix (or mbix). Coordination polymer 1 is a 3-fold-interpenetrated diamondoid network. Particularly, in 1 there occur triple-stranded helices based on Cd ions and bix ligands when viewed along b axis. Coordination polymer 2 is a 2D infinite layer framework, which is further interconnected by hydrogen-bond interactions leading to a 3D supramolecular architecture. Both 3 and 4 feature a 3D open framework with protonated bix (or mbix) locating in the channels, and the 3D open frameworks can be rationalized as a zeolite ABW topology for 3 and pts net for 4. Coordination polymer 5 also has a 3D architecture, and the topological study shows that its framework features a 3D four-connected (6482)(66) net. The photoluminescent properties of the coordination polymers were investigated. All of these coordination polymers exhibited intense fluorescent emissions in the solid state at room temperature. Introduction Great interest has been focused on the rapidly expanding field of the construction of novel functional metal-organic frameworks (MOFs) owing to their variety of intriguing architectures and topologies1 and their potential applications in magnetism, electric conductivity, molecular adsorption, heterogeneous catalysis,2,3 and fluorescent materials.4 Particularly, coordination polymers with fluorescent properties are of great interest for their potential applications as light-emitting diodes (LEDs).4a,5 Metal-organic coordination polymers constructed from aromatic polycarboxylate ligands, such as 1,4-benzenedicarboxylate (H2BDC), 1,3,5-benzenetricarboxylate (H3BTC) and 1,2,4,5benzenetetracarboxylate (H4BTEC), have been extensively studied because of the diversity coordination modes and sensitivity to pH values of the carboxylate groups. In recent years, heterocyclic carboxylic acids such as pyridine-,6 pyrazole,7 and imidazole-carboxylic acids8 have been used as building blocks to investigate the constructions of coordination polymers. Imidazole 4,5-dicarboxylic acid (H3IDC) (Chart 1c) with multifunctional coordination modes can be partially or fully deprotonated to generate H2IDC-, HIDC2-, and IDC3- anions at different pH values.9 H3IDC has the potential for metal coordination generating frameworks containing channels or cavities.8 On the other hand, flexible dipyridyl ligands with certain spacers, for example, 1,2-bis(4-pyridyl)-ethane (bpe),10 1,2-di(4-pyridyl)ethylene (dpe),11 1,3-bi(4-pyridyl)propane (bpp),12 1,4-bis(imidazol-1-ylmethyl)-benzene (bix, Chart 2c),1e,13 and 1,3-bis(imidazol-1-ylmethyl)-benzene (mbix, Chart 2b)13i can freely rotate to meet the requirement of coordination geometries of metal ions in the assembly process. These versatile coordination ligands are able to react with transition metal ions * Corresponding author. Phone: +86-591-83709470. Fax: +86-591-83709470. E-mail: [email protected]. † State Key Laboratory of Structural Chemistry. ‡ Graduate School of Chinese Academy of Sciences.

Chart 1

Chart 2

to produce unique structural motifs with beautiful aesthetics and useful functional properties. It is well-known that the Cd2+ or Zn2+ cations are able to coordinate simultaneously in solution to both oxygen-containing and nitrogen-containing ligands. A great number of cadmium or zinc coordination polymers containing both aromatic carboxylates and N-heterocyclic ligands have been reported. For example, mixed-ligand cadmium or zinc coordination polymers constructed from multivarious aromatic carboxylate ligands and 4,4′-bpy14 or bpp15 have been well explored. Very recently, a series of cadmium or zinc coordination polymers containing carboxylate ligands and rigid 4-bpt (4-bpt ) 3,5-bis(4-pyridyl)4-amino-1,2,4-trizole)16 or 3-bpt (3-bpt ) 3,5-bis(3-pyridyl)4-amino-1,2,4-trizole) ligands17 have been reported. While compared with aforementioned cases, mixed-ligand coordination polymers with aromatic carboxylates and bix or mbix are rarely presented up to now.1e,14a,18 Herein we report five new coordination polymers [Cd(HIDC)(bix)]n (1), [Cd2(BDC)2-

10.1021/cg8002614 CCC: $40.75  2008 American Chemical Society Published on Web 07/23/2008

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Table 1. Crystal Data and Structure Refinement Information for Polymers 1-5

a

polymer

1

2

3

4

5

Empirical formula Formula weight Crystal system Space group a, Å b, Å c, Å R (deg) β (deg) γ (deg) V, Å3 Z Temperature (K) µ(Mo KR), mm-1 Dcal, g/cm3 Reflections collected independent reflections Rint R1,a wR2b [I >2σ(I)] R1,a wR2b (all data) Goodness-of-fit

C19H16CdN6O4 504.78 Orthorhombic P212121 7.6131(5) 10.1340(8) 24.0627(17) 90.00 90.00 90.00 1856.5 (2) 4 293(2) 1.219 1.802 14405 4239 0.0431 0.0403, 0.0784 0.0465, 0.0830 1.135

C30H24Cd2N4O9 809.34 Triclinic P1j 9.963(3) 12.423(4) 12.623(4) 95.171(4) 106.268(5) 95.328(2) 1482.2(8) 2 293(2) 1.497 1.813 11459 6684 0.0159 0.0263, 0.0648 0.0330, 0.0685 1.057

C17H11CdN2O8 483.68 Monoclinic P21/n 7.9105(19) 11.128(3) 19.441(5) 90.00 101.061(2) 90.00 1679.6(7) 4 293(2) 1.353 1.913 12701 3852 0.0204 0.0288, 0.0712 0.0343, 0.0750 1.076

C24H18CdN4O8 602.82 Orthorhombic Pna21 12.9012(7) 14.5816(10) 11.8243(7) 90.00 90.00 90.00 2224.4(2) 4 293(2) 1.044 1.800 16434 4752 0.0152 0.0185, 0.0471 0.0202, 0.0485 1.056

C19H15ZnN4O4 428.72 Monoclinic P21/n 10.8021(9) 10.6244(7) 15.2632(11) 90.00 97.072(4) 90.00 1738.4(2) 4 293(2) 1.449 1.638 13157 3975 0.0456 0.0502, 0.0926 0.0636, 0.0987 1.113

R1 ) Σ|Fo| - |Fc|/Σ|Fo|. b wR2 ) [ Σw(Fo2 - Fc2)2/Σw(Fo2)2]0.5.

(mbix)H2O]n (2), [Cd(HBTEC)(H2bix)0.5]n (3), [Cd(BTEC)(H2mbix)]n (4), and [Zn(BTEC)0.5(mbix)]n (5) (H3IDC ) imidazole 4,5-dicarboxylic acid, H2BDC ) 1,4-benzenedicarboxylate, H4BTEC ) 1,2,4,5-benzenetetracarboxylate, bix ) 1,4-bis(imidazol-1-ylmethyl)-benzene, and mbix ) 1,3-bis(imidazol-1ylmethyl)-benzene), which were constructed from the reaction of Cd2+ (or Zn2+) with mixed ligands of polycarboxylates and bix (or mbix). Experimental Section Materials and General Methods. Bix and mbix were synthesized by the literature method.13a All the other chemicals were commercially available and used as purchased. Thermogravimetric experiments were performed using a TGA/SDTA851 instrument (heating rate of 15 °C/ min, nitrogen stream). IR spectra using KBr pellets were recorded on a Nicolet Magna 750 FT-IR spectrophotometer. Elemental analyses of C, H, and N were determined using an Elementar Vario EL III elemental analyzer. Fluorescence spectra for the solid samples were performed on an Edinburgh Analytical instrument FLS920. Synthesis of [Cd(HIDC)(bix)]n (1). CdCl2 (0.125 mmol, 22.9 mg), H3IDC (0.125 mmol, 19.5 mg), bix (0.25 mmol, 59.5 mg), and H2O (10 mL) were placed in a Teflon-lined stainless steel vessel, and the mixture was sealed and heated to 130 °C for 72 h. The reaction system was cooled to room temperature during 36 h. Colorless prism crystals of 1 were obtained (yield: 38.5 mg, 63% based on CdCl2). Elemental analysis (%): calcd. for C19H16CdN6O4 (504.78): C 45.21, H 3.19, N 16.65; found: C 45.08, H 3.21, N 16.61. IR (KBr, cm-1): 3435s, 3131w, 1735vw, 1611w, 1574s, 1516s, 1478s, 1401s, 1385s, 1307w, 1240s, 1107s, 1085s, 1026w, 790w, 773w, 756w, 727w, 665w, 657w. Synthesis of [Cd2(BDC)2(mbix)(H2O)]n (2). CdCl2 (0.25 mmol, 45.8 mg), H2BDC (0.25 mmol, 41.5 mg), mbix (0.25 mmol, 59.5 mg), and H2O (10 mL) were placed in a Teflon-lined stainless steel vessel, the mixture was sealed and heated to 150 °C for 72 h, and it then was cooled to room temperature during 36 h. Colorless prism crystals of 2 were obtained (yield: 57.2 mg, 56% based on CdCl2). Elemental analysis (%): calcd. for C30H24Cd2N4O9 (809.34) C 44.52, H 2.99, N 6.92; found: C 44.60, H 2.79, N 6.98. IR (KBr, cm-1): 3435m, 3115w, 1567s, 1539s, 1503w, 1385s, 1364s, 1291w, 1244w, 1143w, 1111w, 1087w, 1017w, 838m, 748m, 732w, 659w. Synthesis of [Cd(HBTEC)(H2bix)0.5]n (3). CdCl2 (0.25 mmol, 45.8 mg), H4BTEC (0.25 mmol, 63.5 mg), bix (0.25 mmol, 59.5 mg), and H2O (8 mL) were sealed in a Teflon-lined stainless steel vessel. The mixture was heated to 130 °C for 72 h and cooled to room temperature during 36 h. Colorless prism crystals of 3 were obtained (yield: 57.0 mg, 47% based on CdCl2). Elemental analysis (%): calcd. for C17H11CdN2O8 (483.68) C 42.22, H 2.29, N 5.79; found: C 42.09, H 2.64, N 5.99. IR (KBr, cm-1): 3434w, 3144w, 3068w, 2974w, 2873w,

1956w, 1699m, 1568s, 1538s, 1494m, 1435m, 1392s, 1339m, 1252m, 1175m, 1148w, 1134w, 1105w, 1080w, 872m, 804m, 717m, 627w. Synthesis of [Cd(BTEC)(H2mbix)]n (4). Colorless prism crystals of 4 were obtained in a way similar to 3 except that mbix was used instead of bix (yield: 86.2 mg, 57% based on CdCl2). Elemental analysis (%): calcd. For C24H18CdN4O8 (602.82) C 47.82, H 3.01, N 9.29; found: C 47.51, H 2.82, N 9.24. IR (KBr, cm-1): 34445w, 3141w, 3110w, 3086w, 1592vs, 1538s, 1485m, 1450m, 1410s, 1367vs, 1319m, 1288m, 1237w, 1138m, 1093m, 870m, 850m, 823s, 808m, 726s, 634m 621s, 539w. Synthesis of [Zn(BTEC)0.5(mbix)]n (5). ZnCl2 (0.25 mmol, 34.1 mg), H4BTEC (0.25 mmol, 63.5 mg), mbix (0.50 mmol, 119 mg), and H2O (8 mL) were placed in a Teflon-lined stainless steel vessel, the mixture was sealed and heated to 130 °C for 72 h. Upon cooling to room temperature during 36 h, pale brown prism crystals of 5 were obtained (yield: 46.2 mg, 43% based on ZnCl2). Elemental analysis (%): calcd. for C19H15ZnN4O4 (428.72) C 53.23, H 3.53, N 13.07; found: C 52.40, H 3.60, N 12.65. IR (KBr, cm-1): 3473m, 3118w, 2923w, 1628s, 1610s, 1521w, 1484w, 1446w, 1402w, 1336s, 1301w, 1247w, 1112m, 1086m, 817w, 742m, 723m, 656m. X-Ray Crystallography. X-ray diffraction data were collected on a Rigaku diffractometer with a Mercury CCD area detector (Mo KR; λ ) 0.71073 Å) at 293(2) K. Empirical absorption corrections were applied to the data using the CrystalClear program.19 The structures were solved by the direct method and refined by the full-matrix leastsquares on F2 using the SHELXTL-97 program.20 All of the nonhydrogen atoms were refined anisotropically. The hydrogen atoms of 1 and 2 were treated by geometrical positions or located from difference Fourier maps, whereas those of 3 were all positioned geometrically. As for 4 and 5, the hydrogen atoms were all located in the difference Fourier maps. Crystallographic data and other pertinent information for 1-5 are summarized in table 1. CCDC numbers for coordination polymers 1-5 are 631855-631859, respectively.

Results and Discussion Synthesis and Characterization. All of the coordination polymers described here were synthesized under hydrothermal conditions. They all can be reproducible easily by the hydrothermal techniques. It is well-known that the nature of organic ligands is crucial for the design and construction of desirable metal-organic frameworks. The architectures and functionality of the coordination polymers are strongly influenced by the flexibility, length, coordination ability and symmetry of organic ligands.21,22 We speculated that the flexibility of N-containing ligands may play an important role in structural modulation and topologies manipulation in the self-assembly reactions of

Five d10 3D Metal-Organic Frameworks

polycarboxylates with transition metal ions. Thus, we introduced bix and mbix, which have been considered to be highly flexible N-containing ligands, into the metal-carboxylate system and successfully isolated five metal-organic frameworks containing mixed ligands of polycarboxylates and bix (or mbix). Coordination polymers 1-5, obtained from this mixed-ligand system, exhibit different topologies from one to another. The introduction of bix and mbix initially aimed to act as coligands and to participate in the coordination of transition metal ions. To our surprise, in the cases of 3 and 4, the bix or mbix ligands do not coordinate to the transition metal ions but are protonated and located in the channels as the counterions. In fact, they only serve as structure-directing agents in the formation of 3 and 4. To the best of our knowledge, bix or mbix acting as a template has not yet been reported. It has been well documented that the products of hydrothermal synthesis are significantly affected by the acidity of the reaction conditions.23 Apparently, in the cases of 3 and 4, the reaction systems are more acidic than those in 1 and 2 because one H4BTEC molecule can release four protons at most,24 and as a result, the bix (or mbix) ligands are more likely to be protonated during the reactions.25 Similar situation has been observed in the coordination polymers (H4hpz)[Co3(BTEC)2(H2O)12] · 11H2O and (H4hpz)[Co(BTEC)(H2O)3], in which the H2hpz ligand does not coordinate to the metal ions but acts as a template.26 Furthermore, the nature of metal ions may also influence the results of the self-assembly interactions, as evidenced by the synthesis of 5 where Zn2+ was used instead of Cd2+ and the mbix ligands were not protonated in the final product. The elemental analyses for all the coordination polymers are in good agreement with the theoretical values. Their IR spectra show the characteristic bands of the carboxylic groups in the usual region at 1445-1336 cm-1 for the symmetric vibrations and at 1627-1494 cm-1 for the asymmetric vibrations. The presence of the characteristic bands attributed to the protonated carboxylic groups are observed at 1735 for 1 and 1699 cm-1 for 3, indicating the incomplete deprotonation of the H3IDC and H4BTEC ligands. Description of Crystal Structures. [Cd(HIDC)(bix)]n (1). Single-crystal X-ray diffraction analysis reveals that 1 is a 3-fold-interpenetrated 3D network and crystallizes in the chiral space group P212121 with the flack parameter being 0.03(4). The asymmetric unit shown in Figure 1a contains one Cd ion, one bix, and one HIDC2- anion. There exists one carboxylate group that is not deprotonated. As shown in Figure 1b, the Cd1 center is in a highly distorted trigonal bipyramidal coordination geometry, and is coordinated by two nitrogen atoms from two distinct bix ligands [Cd1-N1b ) 2.359(4), Cd1-N4 ) 2.232(3) Å], two nitrogen atoms from two different HIDC2- [Cd1-N5 ) 2.233(4), Cd1-N6a ) 2.247(4) Å] and one carboxylate oxygen atom in a monodentate mode from HIDC2- [Cd1-O3 ) 2.522(4) Å]. These bond lengths are all in the normal range.18a,27 However, the Cd1-O2a distance is 2.7091(38) Å, indicating a non-negligible interaction, which can be regarded as a semicoordination mode.1e,18a The bidentate bix ligand adopts an anti-conformation coordination mode with the dihedral angle between two terminal imidazole rings being 73.3°. The HIDC2- anion utilizes one carboxylate oxygen atom and two nitrogen atoms adopting a (kN,O-kN′)-µ2 coordination mode, to link Cd1 ions to form a 1D left-handed helical chain with Cd · · · Cd distance of 6.624 Å (Figure 1c). These 1D helical chains are further linked by anti-bix ligands in two directions to form a 3D porous framework (Figure S1, Supporting Information). Taking Cd1 ions as nodes, “long” connections

Crystal Growth & Design, Vol. 8, No. 9, 2008 3347

corresponding to bix bridges, and “short” connections representing HIDC2- anion, the single 3D framework topology represented for 1 is illustrated in Figure 1e. As shown in Figure 1e, the Cd1 ions are four-connected centers and there exist two different hexagonal rings (red and purple) in the single 3D framework. Thus, it can be described as a four-connected topology with Scha¨fli symbol 66. The network can be specified by the vertex symbol of 62•62•62•62•62•62 analyzed by OLEX program,28 which is a typical diamondoid network. It is worthy to point out that the potential tetragonal channels in 1 are filled via interpenetration of two independent identical nets, resulting the formation of a 3-fold parallel interpenetration framework (Figure 1f, the bix ligand and HIDC2- anion have been simplified as lines). Upon interpenetration, the total effective channels become rather limited, and there occur triple-stranded helices based on Cd ions and bix ligands when viewed along b axis (Figure 1d). The flexible bix ligands that adopt an anticonformation coordination mode should play an important role in making the interpenetration possible.13i [Cd2(BDC)2(mbix)(H2O)]n (2). Crystal structure determination of 2 shows that it crystallizes in the space group P1j and reveals a 3D supramolecular architecture with channels arising from 2D layers extended by hydrogen bonds. The asymmetric unit of 2 is shown in Figure 2a, which consists of two Cd ions, one mbix, two BDC2-, and one coordinated water molecule. As depicted in Figure 2b, there are two types of coordination environments around the Cd ions in the crystal structure and both hepta coordinated. Cd1 is in a badly distorted pentagonal bipyramidal coordination geometry, which is defined by one carboxylate oxygen atom [Cd1-O7b ) 2.4560(19) Å] and one aqua ligand [Cd1-O9 ) 2.392(2) Å] occupying the apical positions, whereas the basal plane is completed by one mbix nitrogen atom [Cd1-N4a ) 2.251(2) Å] and four oxygen atoms [Cd1-O1 ) 2.2064(17) Å, Cd1-O2 ) 2.616(2) Å, Cd1-O5 ) 2.3800(18) Å, Cd1-O6 ) 2.4636(18) Å] from two different carboxylate groups of BDC2- ligands. Cd2 is surrounded by six carboxylate oxygen atoms [Cd2-O5 ) 2.4544(17) Å, Cd2-O4d ) 2.4929(19) Å, Cd2-O3c ) 2.3698(18) Å, Cd2-O4c ) 2.3940(19) Å, Cd2-O7b ) 2.396(2) Å, Cd2-O8b ) 2.3502(19) Å] from four different BDC2- ligands and one nitrogen atom [Cd2-N1 ) 2.2366(19) Å] from one mbix, also in a highly distorted pentagonal bipyramidal geometry. The mbix ligands adopt a syn-conformation coordination mode to connect two Cd ions at intervals of one Cd ion with the dihedral angle between two terminal imidazole rings being 24.57°. The two different BDC2- ligands display k2-(k2-µ2)-µ3 and 2 (k -µ2)-(k2-µ2)-µ4 coordination modes, respectively (Chart 3a). They alternately connect the Cd ions in two directions to make up of a 2D layer structure (Figure 2c). Strong hydrogen-bond interactions occur between the adjacent layers which arise from the coordinated water and carboxylate oxygen atoms (O2) with the separation of O9-H9a-O2 being 2.722(3) Å. Thus, these resulting 2D layer structures are further linked by the hydrogenbond interactions leading to the formation of a 3D supramolecular architecture (Figure S2, Supporting Information). [Cd(HBTEC)(H2bix)0.5]n (3). X-ray diffraction studies reveal that 3 crystallizes in the monoclinic space group P21/n. The asymmetric unit of 3 consists of one Cd ion, one HBTEC3-, and one protonated bix ligand. There exists a protonated carboxylate group that is not coordinated to the metal centers (Figure 3a). The local coordination environment around Cd1 ion is shown in Figure 3b, where the coordination of Cd1 ion is in a highly distorted octahedral geometry. One bidentate carboxylate oxygen atom [Cd1-O6b ) 2.2503(19) Å] and one

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Figure 1. (a) View of the asymmetric unit of 1. Hydrogen atoms belonged to C atoms are omitted for clarity. (b) View of the coordination environment of Cd ion in 1. Hydrogen atoms are omitted for clarity. Symmetry codes: a 2-x, 0.5+y, -0.5-z; b 1.5+x, 1.5-y, -z. (c) View of the 1D lefthanded helical chain based on Cd ions and HIDC2- between bix ligands in 1. (d) View of triple-stranded helices based on Cd ions and bix ligands in 1. Wire diagram (left) and space-filling diagram (right). (e) Topological view showing the individual diamondoid network for 1 at b-axis. (f) Schematic view showing the 3-fold-interpenetrated 3D topological network for 1 along b axis.

chelating carboxylate oxygen atom [Cd1-O2 ) 2.398(2) Å] occupytheaxialpositionsoftheoctahedronwiththeO2-Cd1-O6b bond angle of 150.87(7)°. The equatorial plane of the distorted octahedral sphere is defined by one chelating carboxylate group [Cd1-O7c ) 2.461(2) Å, Cd1-O8c ) 2.318(2) Å], one chelating carboxylate oxygen atom [Cd1-O1 ) 2.336(2) Å] and one bidentate carboxylate oxygen atom [Cd1-O5a ) 2.2459(19) Å]. The Cd1 center is approximately coplanar with the mean plane of the four equatorial atoms with a deviation of 0.1134 Å. The HBTEC3- ligand acts as a tetraconnector through

two chelating carboxylate groups and one bidentate carboxylate group (Chart 3b) linking Cd1 ions into a three-dimensional anionic framework with large channels when viewed along a axis. The protonated bix ligands which show anti-conformation mode are located in the channels, with the two terminal imidazole rings being in a parallel fashion, as shown in Figure S3 (Supporting Information). Taking Cd1 ions and HBTEC3ligands as four-connected nodes (regarding HBTEC3- ligand as a simple pellet), the overall anionic framework topology for 3 can be defined as (Cd1)(HBTEC) with the Scha¨fli symbol of

Five d10 3D Metal-Organic Frameworks

Figure 2. (a) View of the asymmetric unit of 2. Hydrogen atoms are omitted for clarity. (b) View of the coordination environment of Cd ions in 2. Hydrogen atoms are omitted for clarity. Symmetry codes: a 3-x, 3-y, 1-z; b 1+x, y, z; c -1+x, y, -1+z; d 4-x, 3-y, 2-z. (c) View of the 2D layer structure constructed by Cd ions and BDC2along b axis in 2.

Chart 3. Coordination modes of BDC2- in 2 (a), HBTEC3in 3 (b), and BTEC4- in 4 (c)

(42638)(42638) (Figure 3c). When further analyzed by OLEX program,28 the vertex symbols of the two nodes are both 4•6•6•4•6•82, so the anionic framework in 3 can be simply regarded as a uninodal four-connected net with a Scha¨fli symbol of (42638). Thus, this net can be ascribed to a zeolite ABW topology.29 As for the structure of a zeolite ABW, the network of 3 also contains eight-membered channels which are formed from four metal centers and four HBTEC3- ligands. Replace-

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Figure 3. (a) View of the asymmetric unit of 3. Hydrogen atoms belonged to C atoms are omitted for clarity. (b) View of the coordination environment of Cd ion in 3. Hydrogen atoms are omitted for clarity. Symmetry codes: a 2.5-x, -0.5+y, 0.5-z; b -0.5+x, 0.5-y, -0.5+z; c 1.5-x, -0.5+y, 0.5-z. (c) Topological view showing the equivalent 3D framework for 3 at a axis (the protonated bix ligands have been omitted for clarity, the purple pellets stand for HBTEC3-).

ment of the four-connected centers of zeolite ABW, Si and Al, with the Cd2+ ions and HBTEC3- ligands, replicates and expands the 3.4 × 3.8 Å2 eight-membered channels to approximately 11.9 × 17.6 Å2.30 [Cd(BTEC)(H2mbix)]n (4). Coordination polymer 4 crystallizes in the orthorhombic space group Pna21. Its asymmetry unit contains one Cd ion, one BTEC4- and one protonated mbix ligand (Figure 4a). As shown in Figure 4b, the Cd1 atom is coordinated to two chelating carboxylate groups from two separated BTEC4- ligands [Cd1-O1 ) 2.529(2) Å, Cd1-O2 ) 2.3554(14) Å, Cd1-O7c ) 2.5425(17) Å, Cd1-O8c ) 2.3312(17) Å] and two monodentate carboxylate oxygen atoms from two individual BTEC4- ligands [Cd1-O4a ) 2.2218(17) Å, Cd1-O5b ) 2.2724(17) Å]. The coordination environment of the Cd1 atom can be regarded as a distorted octahedron,

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Figure 4. (a) View of the asymmetric unit of 4. Hydrogen atoms belonged to C atoms are omitted for clarity. (b) View of the coordination environment of Cd ion in 4. Hydrogen atoms are omitted for clarity. Symmetry codes: a x+1/2, -y+1/2, z; b -x+1/2, y+1/2, z-1/2; c -x+1, -y, z-1/2. (c) Topological view showing the equivalent 3D framework for 4 along a axis (the protonated mbix ligands have been omitted for clarity, the purple pellets stand for the BTEC4-).

which is similar to that in 3. The equatorial plane of the distorted octahedron is composed of O1, O2, O7c and O5b, while the axial positions are occupied by O4a and O8c with the O4a-Cd1-O8c bond angle of 134.44(5)°. The Cd1 center is approximately coplanar with the mean plane of the four equatorial atoms with a deviation of 0.0329 Å. The BTEC4ligand acts as a tetraconnector through two chelating carboxylate and two monodentate carboxylate groups (Chart 3c), which bridge Cd1 ions into a three-dimensional anionic framework with large channels when viewed along a-axis. Similar to 3, the protonated mbix ligands are located in the channels and they adopt syn-conformation mode with the dihedral angle between two terminal imidazole rings being 30.68°, as shown in Figure S4 (Supporting Information). Strong hydrogen bonds are observed between the protonated mbix ligands and two chelating carboxylate oxygen atoms with the separations of N1-H1-O2 and N4-H4-O8 being 2.768(3) and 2.683(3) Å, respectively.

Lin et al.

Both the Cd1 ion and BTEC4- ligand are four-connected centers when viewing Cd1 ions and BTEC4- ligands as nodes (simplifying the BTEC4- as a pellet). Thus, the overall topology of 4 can be defined as (Cd1)(BTEC) with the Scha¨fli symbol of (4284)(4284), as illustrated in Figure 4c. The topological analysis of 4 has been performed on OLEX program28 giving the vertex symbols of the two nodes as 4•4•87•87•87•87 and 4•4•88•88•82•82, respectively. According to O’Keeffe, this net with Schla¨fli symbol (4284)(4284) is named as a pts net.31 Comparing 4 with 3, where both the protonated mbix and bix ligands act as templates, different frameworks and topologies are emerged in these coordination polymers. In 3, the triply deprotonated HBTEC3- ligand employs three carboxylate groups, adopting a (k2)-(k2)-(k1-k1)-µ4 coordination mode (Chart 3b), to construct the anionic framework. Whereas in 4, the coordination mode of the quadruply deprotonated BTEC4ligand is (k2)-(k2)-(k1)-(k1)-µ4 (Chart 3c), utilizing all the four carboxylate groups to fabricate the anionic framework. According to our investigation in Cambridge Crystallographic Data Centre (CCDC), these coordination modes of H4BTEC have not been observed for the metal-H4BTEC coordination polymers. However, they are proximal to the (k2)-(k1-k1)-(k1-k1)-(k2)-µ6 coordination mode of H4BTEC reported by Hong, etc.24 This difference in the coordination mode of the carboxylate groups is responsible for the distinct crystal systems crystallized in 3 and 4. We think that the flexibility and symmetry of the template ligands should finetune the formation of coordination polymers resulting in diverse frameworks. [Zn(BTEC)0.5(mbix)]n (5). Coordination polymer 5 also has a 3D architecture, which crystallizes in the space group P1j. The asymmetric unit comprises of one Zn ion, half-a BTEC4- ligand and one mbix ligand, as shown in Figure 5a. The Zn1 atom is in a deviated tetrahedron environment, coordinated by two carboxylate oxygen atoms in a monodentate fashion from two different BTEC4- ligands [Zn1-O3 ) 1.952(2), Zn1-O2a ) 1.9742(19) Å] and two nitrogen atoms from two distinct mbix ligands [Zn1-N1 ) 2.008(3) Å, Zn1-N4b ) 2.004(3) Å], as depicted in Figure 5b. All the bond lengths around the Zn1 center are within the normal range.9,1e The completely deprotonated H4BTEC ligand, adopting a (k1)-(k1)-(k1)-(k1)-µ4 coordination mode, plays a four-connected role in linking four Zn2+ centers to form a 2D layer network with (4, 4) topology (Figure 5c). The mbix ligands bridge the metal centers of the 2D layered networks in an anti-conformation to build up a 3D pillared framework (Figure S5, Supporting Information). The dihedral angle between two terminal imidazole rings is 60.12°. There are two kinds of nodes in the structure of 5: one is a fourconnected node for Zn1 and the other is a four-connected node for BTEC4- ligand. The ratio of these two kinds of nodes is 1:1 (Zn1/BTEC). If the mbix ligand is simplified as a line connecting the metal centers, the framework of 5 can be symbolized as a (6482)(66) network (Figure 5d). The net is analyzed by OLEX program28 and the results show that the vertex symbols of these two nodes can be described as 63•63•63•63•82•* and 62•62•62•62•62•62, respectively. In a search of RCSR database,31 the most related net to 5 is bbf net, which shows a Schla¨fli symbol of (6482)(66)2 with the vertex symbols of the nodes being 62•62•62•62•84•84 and 6•6•6•6•62•62, respectively. Although 4 and 5 have been obtained under similar hydrothermal conditions, their frameworks and topologies are different. The Cd1 ions in 4 are six-coordinated and the mbix ligands are protonated locating in the channels, whereas the Zn1 ions in 5 are four-coordinated and the mbix ligands act as pillars to participate in the construction of the 3D framework.

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Crystal Growth & Design, Vol. 8, No. 9, 2008 3351

Figure 5. (a) View of the asymmetric unit of 5. Hydrogen atoms are omitted for clarity. (b) View of the coordination environment of Zn ion in 5. Hydrogen atoms are omitted for clarity. Symmetry codes: a x+0.5, 0.5-y, z+0.5; b -1+x, y, z; c -0.5+x, 0.5-y, -0.5+z; d x+1, y, z; e 3-x, -y, 1-z; f 3.5-x, -0.5+y, 1.5-z. (c) View of the 2D layer structure constructed from Zn ions and BTEC4- in 5 (top) and a schematic view showing the equivalent 2D network for 5 (bottom) (the purple pellets stand for BTEC4-). (d) Topological views showing the equivalent 3D framework for 5 along bc plane (the purple pellets stand for BTEC4-, the red lines stand for mbix).

Thermal Stability Analyses. The thermal stability of 1-5 was examined by TGA in a nitrogen atmosphere (Figure S6, Supporting Information). The TGA curve of 1 indicates that there is no significant loss up to about 330 °C. Then a sharp weight-loss step was observed between 330 and 750 °C, which can be attributed to the decomposition of organic ligands. The TGA curve of 2 reveals a weight loss of 2.56% from 180 to 284 °C, which can be assigned to the weight loss of the coordinated water molecule (calcd ) 2.22%). Coordination polymer 2 is stable up to 380 °C, from which the decomposition of the framework starts. In the TGA curves for 3 and 4, there are no weight loss and phase transition from room temperature to 300 °C. For 5, it is stable up to 380 °C, from which the framework begins to collapse. Luminescent Properties. Previous studies have shown that coordination polymers containing cadmium and zinc ions exhibit photoluminescent properties.4a,b,6j,9,8o,18a,32 Thus, the photoluminescent properties of 1-5 in the solid state at room

temperature have been investigated. As illustrated in Figure 6, the intense broad emission bands at 456 nm (λex ) 366 nm) for 1, 439 nm (λex ) 330 nm) for 2, 457 nm (λex ) 330 nm) for 3, 425 nm (λex ) 320 nm) for 4, and 436 nm (λex ) 360 nm) for 5 are observed. For excitation wavelengths between 280 and 480 nm, there is no obvious emission observed for free H3IDC ligand under the same experimental conditions,8m,o,9,32 while free bix ligand presents a photoluminescence emission at 392 nm (λex ) 340 nm).13i Therefore, the fluorescent emission of 1 may be proposed to originate from the coordination of HIDC2to the cadmium atom (ligand-to-metal charge transition, LMCT).8m,o,9,33 According to the reported literature, the free H2BDC, H4BTEC and mbix exhibit fluorescent emission bands at 393 nm (λex ) 347 nm),4c 342 nm (λex ) 308 nm),34 and 395 nm (λex ) 334 nm),13i respectively. Taking the emission bands of these free organic ligands into consideration, the emissions of 2-5 may also be assigned as ligand-to-metal charge transition (LMCT). These coordination polymers may

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Lin et al.

Note Added after ASAP Publication. This article was published ASAP on July 23, 2008. A change has been made in paragraph (3) of the Results and Discussion Section. The correct version was published on July 29, 2008.

References

Figure 6. Solid-state photoluminescence spectra of 1 (λex ) 366 nm), 2 (λex ) 330 nm), 3 (λex ) 330 nm), 4 (λex ) 320 nm), and 5 (λex ) 360 nm) at room temperature.

be excellent candidates for potential photoactive materials because they are highly thermally stable. Conclusion In summary, we have successfully isolated five new coordination polymers resulting from aromatic polycarboxylate acids and Cd ions in the presence of flexible imidazole-based ligands. All coordination polymers have been characterized by elemental analysis, FT-IR spectra, thermal analysis, and single-crystal X-ray diffraction studies. They all features 3D frameworks, which can be abstracted as different topology architectures. The polycarboxylate acids employed in this work display their characteristic distinct coordination modes of which the coordination modes of H4BTEC in 3 and 4 are unprecedented. Besides, bix in 1, H2bix in 3, and mbix in 5 reveal anticonformation, while mbix in 2 and H2mbix in 4 show synconformation. The dihedral angles between two terminal imidazole rings of bix (or H2bix) and mbix (or H2mbix) vary from one to another in these five coordination polymers. The diversity of these dihedral angles should be ascribed to the high flexibility of the two N-containing ligands. In the formation of 3 and 4, the bix and mbix are protonated and serve as templates locating in the channels of the frameworks. This work demonstrates that the different coordination modes of the polycarboxylate acids and the flexibilities of bix and mbix ligands may exert an important influence on the formation of resulting diverse frameworks. They are all highly thermally stable and display strong emission bands in the solid state at room temperature. Therefore, they appear to be good candidates for novel hybrid inorganic-organic photoactive materials. Acknowledgment. This work was supported by the grants from the State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences (CAS, SZD08002-2), National Basic Research Program of China (973 Program, 2007CB815306), and the National Natural Science Foundation of China (20733003 and 20673117). Supporting Information Available: FT-IR spectra, TGA curves, X-ray crystallographic information files for 1-5, and figures of 3D structures of 1-5. This information is available free of charge via the Internet at http://pubs.acs.org.

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CG8002614