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Polycatenated bilayer motif constructed from flexible N, N′-bipyridyl and aromatic dicarboxylate ligands
Inorganic Chemistry Communications 15 (2012) 1–4
Contents lists available at SciVerse ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
Polycatenated bilayer motif constructed from flexible N, N′-bipyridyl and aromatic dicarboxylate ligands Xin Zhang a, Zhao-Ji Li a, Ye-Yan Qin a, b, Yuan-Gen Yao a,⁎ a b
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China Graduate School, Chinese Academy of Sciences, Beijing 100039, People's Republic of China
a r t i c l e
i n f o
Article history: Received 16 June 2011 Accepted 24 August 2011 Available online 5 September 2011 Keywords: Luminescent compound Double layer Parallel fashion Polycatenation
a b s t r a c t A luminescent compound, [Cd (HO-BDC) (bpe)1.5]n (1 HO-H2BDC=5-hydroxyisophthalic acid, bpe=1,2-bis (4-pyridyl) ethane), was hydrothermally synthesized. It features a 5-connected two-dimensional (2D) double layer motif. Interestingly, this 2D double layer motif is further interlocked with the neighboring ones in the parallel fashion, giving rise to the final three-dimensional (3D) polycatenated network. Moreover, the title compound exhibits intense yellow photoluminescence at room temperature. © 2011 Published by Elsevier B.V.
Design and construction of coordination polymers with fascinating architectures and topologies and potential applications as functional solid materials have aroused great interest of chemists [1–3]. Under this background, a great number of novel metal-organic frameworks (MOFs) have been constructed from metal centers with well-defined coordination geometries and multifunctional organic ligands containing N- and/or O-donors under hydro (solvo) thermal conditions [2–5]. Among these, what are particularly attractive are the entangled systems, such as interpenetrated networks, polycatenated and polyknotted species, as well as polythreading and so on. The characteristics of various entangled systems have been well discussed in comprehensive reviews by Carlucci [4]. According to Carlucci et al., polycatenation as a subgroup of entangled systems differs from the other entangled systems. The main feature of the polycatenation is that the whole catenated array has a higher dimensionality than that of each individual component motif. Moreover, each individual motif is catenated only with the adjacent ones and not with all the others [4]. These catenated individual motifs can be 0D, 1D, 2D, 3D frameworks with closed loops, which are interlocked via topological Hopf links to give rise to the final higher dimensional polycatenated network [5]. More recently, there are great numbers of examples of polycatenation based on metal-organic frameworks [6,7]. However, to the best of our knowledge, such parallel polycatenation of bilayer motif with cuboidal box as building subunit remains rarely be reported. One of the rational strategies to construct such polycatenated network is the judicious selection of conformationally nonrigid organic
⁎ Corresponding author. Tel.: + 86 591 83711523; fax: + 86 591 83714946. E-mail address: [email protected] (Y.-G. Yao). 1387-7003/$ – see front matter © 2011 Published by Elsevier B.V. doi:10.1016/j.inoche.2011.08.023
ligands since these flexible ligands with appropriate spacers have already proven a certain ability to construct uncommon polycatenation network mainly due to their diverse conformations in the selfassembly process [8]. The mixture of flexible 1,2-bis (4-pyridyl)ethane (bpe) and rigid aromatic carboxylate ligands has been widely used to construct MOFs. Most of them are interpenetrated frameworks [9], but the polycatenated MOFs are still rare. Herein, we describe the reaction of cadmium(II) nitrate, OH-H2BDC and bpe that gives rise to a parallel polycatenation network containing an individual 5-connected bilayer motif [Cd (HO-BDC) (bpe)1.5]n. Moreover, this compound exhibits intense yellow luminescence at room temperature. A mixture of Cd(NO3)2⋅4H2O (0.5 mmol, 0.154 g), HO-H2BDC (0.5 mmol, 0.105 g) and bpe (0.5 mmol, 0.092 g) in 12 ml mixed solvent of H2O and EtOH (V/V=5:1) was stirred for 30 min at room temperature, and then the reaction mixture was sealed in a Teflon-lined reactor and kept at 160 °C for 72 h under autogenous pressure. After being slowly cooled to the room temperature, brown crystals [10] were obtained in 55% yield (based on Cd). Compound 1 was identified by satisfactory elemental analysis, IR spectroscopy (Fig. S7), powder X-ray diffraction and single-crystal X-ray diffraction [11]. Single-crystal X-ray structural analysis shows that compound 1 features a 2D double layer structure with large channels along crystallographic a axis (Fig. S1). The fundamental unit is shown in Fig. 1; there are one crystallographic independent Cd(II) ion, one HO-BDC anion, one and a half bpe ligands. Each Cd(II) ion is seven-coordinated and can be described as a distorted {CdN3O4} pentagonal bipyramid geometry. Two pairs of chelating carboxylate O donors from different HO-BDC ligands and one pyridyl N donor from a bpe ligand comprise the equatorial plane; two pyridyl N donors from another two bpe ligands occupy
2
X. Zhang et al. / Inorganic Chemistry Communications 15 (2012) 1–4
Fig. 1. Coordination environment around Cd(II) ion. All hydrogen atoms attached to carbon atoms were omitted for clarity. Symmetry codes: (A) 1 + x, y, z; (B) x, y, − 1 + z.
the remaining axial sites [N1–Cd1–N2B= 174.425(2)°]. The Cd–O and Cd–N distances are in the range of 2.278(5)–2.667(7) Å and 2.326(4)– 2.385(5) Å, respectively, which are in accordance with Cd(II) polymers previously reported [12]. Interestingly, bpe ligands use their end N donors bridging different Cd(II) ions with the Cd⋅⋅⋅Cd separation of 13.947(5) and 14.010(9) Å, respectively, giving rise to a 1D infinite cationic {[Cd2(bpe)3]4+}n ladder chain propagating along c axis (Fig. 2a). The HO-BDC anions act as chelating bis-bidentate ligands and bridge the neighboring parallel cationic ladder chains into a neutral 2D double layer motif (Fig. 2b). From a topological viewpoint, this 2D double layer motif can be simplified into a (4,5) net by viewing metal centers as nodes and organic spacers as linkers (Fig. 2c). A prominent structural feature of 1 is the existence of cuboidal box of {Cd8(bpe)8(HOip)4} in the double layer structure (Fig. S1). Each cuboidal box consists of eight Cd(II) ions at the corners connected
by eight long bpe ligands and four HO-BDC ligands, which make up the 12 edges of the cuboidal box. The approximate dimension of the cuboidal box is 14.010 × 13.947 × 10.282 Å. Viewing along the a axis, very large regular square channels are evident in the single bilayer motif (Fig. S2). Although large channels exit in the single double layer motif, they are interpenetrated by the identical bilayer motifs. Thus, the most fascinating structural feature of 1 is that each 5-connected 2D double layer motif, which is parallel to each other, is interlocked with the adjacent identical ones. Therefore, the resulting 3D array is an infinite polycatenation of the 2D double layer motif (Fig. 3). The catenation occurs between the bpe ligand and cavum of the cuboidal box (Fig. S3). Although some examples of polycatenated MOFs have been reported [13], to the best of our knowledge, such kind of 2D + 2D → 3D polycatenation of the bilayer motif has not been observed previously in seven-coordinated cadmium(II) polymers. The experimental powder X-ray diffraction (PXRD) pattern of 1 agrees well with the simulated one based on the single-crystal Xray diffraction data (Fig. S4), suggesting that it is in pure phase. To study the stability of the title compound, thermogravimetric analysis (TGA) was performed on a polycrystalline sample of this compound. No obvious weight loss was observed in the temperature range of 30–167 °C. Upon heating above 167 °C, decomposing started and significant weight loss occurred, indicating that the whole framework can be stable up to 167 °C (Fig. S5). The solid-state photoluminescent properties of compound 1 have been investigated at room temperature and the emission and excitation spectra are shown in Fig. 4. It can be observed that intense emission occurred at 542 nm upon excitation of 432 nm for 1 (Fig. S6). In order to ascertain the ascription of the emission band, we referred to many literatures and found that the aromatic dicarboxylate ligand and N, N′bipyridyl ligand are nearly nonfluorescent in the range of 400–600 nm at ambient temperature [9a]. Thus, the emission of 1 may be assigned to the ligand-to-metal-charge-transfer (LMCT). In summary, an interesting luminescent cadmium polymer has been successfully synthesized under hydrothermal conditions. It features a 5connected 2D bilayer motif. Moreover, this 2D bilayer motif is further interlocked with each other, thus generating the final 3D polycatenation array.
Fig. 2. (a) 1D infinite cationic {[Cd2(bpe)3]4+}n ladders along c axis. (b) 2D bilayer motif. (c) Schematic representation of the 5-connected bilayer motif (yellow atoms: Cd centers; purple bonds: HO-BDC ligands; green bonds: bpe ligands).
X. Zhang et al. / Inorganic Chemistry Communications 15 (2012) 1–4
3
Fig. 3. (a) Parallel polycatenation of the 5-connected bilayer motif. (b) Schematic representation of the polycatenated 5-connected bilayer.
Fig. 4. Emission spectrum 1 in the solid-state at room temperature.
Acknowledgements This work was supported by 973 Program of China (2011CBA00505), the Chinese Academy of Sciences (KJCX2-YW-H30, KGCX2-YW-222 and KJCX2-YW-M10) and the Science Foundation of the Fujian Province (2009HZ0005-1 and 2006L2005).
Appendix A. Supplementary data CCDC NO. 802446; contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic data Center Via http://www.ccdc. cam.ac.uk/data_request/cif. TGA and powder X-ray patterns can be found in the supporting file. Supplementary data to this article can be found online at doi:10.1016/j.inoche.2011.08.023.
References [1] (a) B. Moulton, M.J. Zaworotko, From molecules to crystal engineering: supramolecular isomeric and polymorphism in network solids, Chemical Reviews 101 (2001) 1629–1658; (b) O.R. Evans, W.B. Lin, Crystal engineering of NLO materials based on metalorganic coordination networks, Accounts of Chemical Research 35 (2002) 511–522. [2] (a) S. Kitagawa, R. Kitaura, S.I. Noro, Functional porous coordination polymers, Angew Chemie International Edition 43 (2004) 2334–2375; (b) C. Janiak, Engineering coordination polymers towards applications, Dalton Transactions (2003) 2781–2804.
[3] (a) J. Zhang, Y.C. Shen, Y.Y. Qin, Z.J. Li, Y.G. Yao, Polycatenated 3-connected hydrogenbonding bilayer stabilized by argentophilic interactions, CrystEngComm 9 (2007) 636–638; (b) R.G. Xiong, X.Z. You, B.F. Abrahams, Z. Xue, C.M. Che, Enantioseparation of racemic organic molecules by a zeolite analogue, Angewandte Chemie, International Edition 40 (2001) 4422–4425; (c) J. Tao, Y. Zhang, M.L. Tong, X.M. Chen, T. Yuen, C.L. Lin, X.Y. Huang, J. Li, A mixed-valence copper coordination polymer generated by hydrothermal metal/ligand redox reactions, Chemie Common (2002) 1342–1343. [4] L. Carlucci, G. Ciani, D.M. Proserpio, Borromean links and other non-conventional links in ‘polycatenated’ coordination polymers: re-examination of some puzzling networks, CrystEngComm 5 (2003) 269–279. [5] L. Carlucci, G. Ciani, D.M. Proserpio, Polycatenation, polythreading and polyknotting in coordination network chemistry, Coordination Chemistry Reviews 246 (2003) 247–289. [6] (a) S.M. Chen, J. Zhang, C.Z. Lu, One-pot synthesis of two isomeric zinc complexes with unusual polycatenation motifs, CrystEngComm 9 (2007) 390–393; (b) X.M. Zhang, X.-M. Chen, A new porous 3-D framework constructed from fivefold parallel interpenetration of 2-D (6, 3) nets: A mixed-valence copper (I,II) coordination polymer [CuI2CuII(4,4′-bpy)2(pydc)2]·4H2O, European Journal of Inorganic Chemistry (2003) 413–417. [7] (a) L. Carlucci, G. Ciani, P. Macchi, D.M. Proserpio, S. Rizzato, Complex interwoven polymeric frameworks from the self-assembly of silver(I) cations and sebaconitrile, Chemistry A European Journal 5 (1999) 237–243; (b) J.Y. Lu, A.M. Babb, Cu3(bpen)(IN)6(H2O)2, Inorganic Chemistry 40 (2001) 3261–3262; (c) M.L. Tong, X.M. Chen, B.H. Ye, L.N. Ji, Self-assembly three-dimensional coordination polymers with unusual ligand-unsupported Ag–Ag bonds: syntheses, structures, and luminescent properties, Angewandte Chemie, International Edition 38 (1999) 2237–2240. [8] (a) Y.H. Wen, J. Zhang, X.Q. Wang, Y.L. Feng, J.K. Cheng, Z.J. Li, Y.G. Yao, A rare metalorganic 3D architecture with a pseudo-primitive cubic topology with double edges constructed from a 12-connected SBU, New Journal of Chemistry 29 (2005) 995–997; (b) J. Zhang, Y.B. Chen, Z.J. Li, Y.Y. Qin, Y.G. Yao, Zn (BDC) (BPP) Cl2, Inorganic Chemistry Communications 9 (2006) 449–451. [9] (a) X.J. Li, R. Cao, D.F. Sun, W.H. Bi, Y.Q. Wang, X. Li, M.C. Hong, Synthesis and characterizations of zinc(II) compounds containing three-dimensional interpenetrating diamondoid networks constructed by mixed ligands, Crystal Growth and Design 4 (2004) 775–780; (b) F.A. Alimeida Paz, J. Klinowski, Synthesis and characterization of a novel cadmium-organic framework with trimesic acid and 1,2-bis(4-pyridyl)ethane, Inorganic Chemistry 43 (2004) 3948–3954. [10] Anal. Calcd. for C26H28N3O8Cd: C, 50.09%; H, 4.50%; N, 6.74%. Found: C, 50.12%; H, 4.38%; N, 6.69%. IR (KBr pellet cm− 1): 3059(w), 1952(w), 1681(w), 1611(s), 1560(s), 1502(m), 1371(s), 1271(w), 1225(m), 1129(w), 1092(w), 1071(m), 1014(m), 975(w), 886(w), 814(w). [11] Crystal data of 1: C26H22N3O5Cd, Mr = 568.88, brown crystal, triclinic, space group Pī, a = 10.2817(5) Å, b = 10.8136(5) Å, c = 13.9466(5) Å, β = 97.447(3)°, V = 1363.37(10) Å3, Z = 2, T = 293(2) K, Dc = 1.386 g cm− 3, μ = 0.853 mm− 1, R (wR) = 0.0571 (0.1666) and GOF = 1.081 for 4196 reflections with I N 2σ(I); The crystal structure of 1 was solved by direct method and refined by full-matrix least-squares using the SHELXTL-97 program. All non-hydrogen atoms of 1 were refined with anistropic temperature parameters, and all the hydrogen atoms attached to carbon were fixed at their ideal positions. [12] (a) L. Carlucci, G. Ciani, D.M. Proserpio, S. Rizzato, New polymeric networks from the self-assembly of silver(I) salts and flexible ligand 1,3-bis(4-pyridyl) propane (bpp). A systematic investigation of the effects of the counterions
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and survey of the coordination polymers based on bpp, CrystEngComm 4 (2002) 121–129; (b) J.C. Dai, X.T. Wu, S.M. Hu, Z.Y. Fu, J.J. Zhang, W.X. Du, H.H. Zhang, R.Q. Sun, Crystal engineering of the coordination architecture of metal polycarboxylate complexes by hydrothermal synthesis: assembly and characterization of four novel cadmium polycarboxylate coordination polymers based on mixed ligands, European Journal of Inorganic Chemistry (2004) 2096–2106. [13] (a) D.J. Chesnut, A. Kusnetzow, R. Birge, J. Zubieta, Ligand influence on copper cyanide solider-state architecture: flattened and fused “slinky”, corrugated
sheet, and ribbon motifs in the copper–cyanide-triazolate-organoamine family, Inorganic Chemistry 38 (1999) 5484–5494; (b) X.L. Wang, C. Qin, E.B. Wang, Y.G. Li, Z.M. Su, L. Xu, L. Carlucci, Entangled coordination networks with inherent features of polycatenation, polythreading, and polyknotting, Angew, Chem. Int. Ed. 44 (2005) 5824–5827; (c) S.R. Batten, Topology of interpenetration, CrystEngComm 3 (2001) 67–72.
Contents lists available at SciVerse ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
Polycatenated bilayer motif constructed from flexible N, N′-bipyridyl and aromatic dicarboxylate ligands Xin Zhang a, Zhao-Ji Li a, Ye-Yan Qin a, b, Yuan-Gen Yao a,⁎ a b
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China Graduate School, Chinese Academy of Sciences, Beijing 100039, People's Republic of China
a r t i c l e
i n f o
Article history: Received 16 June 2011 Accepted 24 August 2011 Available online 5 September 2011 Keywords: Luminescent compound Double layer Parallel fashion Polycatenation
a b s t r a c t A luminescent compound, [Cd (HO-BDC) (bpe)1.5]n (1 HO-H2BDC=5-hydroxyisophthalic acid, bpe=1,2-bis (4-pyridyl) ethane), was hydrothermally synthesized. It features a 5-connected two-dimensional (2D) double layer motif. Interestingly, this 2D double layer motif is further interlocked with the neighboring ones in the parallel fashion, giving rise to the final three-dimensional (3D) polycatenated network. Moreover, the title compound exhibits intense yellow photoluminescence at room temperature. © 2011 Published by Elsevier B.V.
Design and construction of coordination polymers with fascinating architectures and topologies and potential applications as functional solid materials have aroused great interest of chemists [1–3]. Under this background, a great number of novel metal-organic frameworks (MOFs) have been constructed from metal centers with well-defined coordination geometries and multifunctional organic ligands containing N- and/or O-donors under hydro (solvo) thermal conditions [2–5]. Among these, what are particularly attractive are the entangled systems, such as interpenetrated networks, polycatenated and polyknotted species, as well as polythreading and so on. The characteristics of various entangled systems have been well discussed in comprehensive reviews by Carlucci [4]. According to Carlucci et al., polycatenation as a subgroup of entangled systems differs from the other entangled systems. The main feature of the polycatenation is that the whole catenated array has a higher dimensionality than that of each individual component motif. Moreover, each individual motif is catenated only with the adjacent ones and not with all the others [4]. These catenated individual motifs can be 0D, 1D, 2D, 3D frameworks with closed loops, which are interlocked via topological Hopf links to give rise to the final higher dimensional polycatenated network [5]. More recently, there are great numbers of examples of polycatenation based on metal-organic frameworks [6,7]. However, to the best of our knowledge, such parallel polycatenation of bilayer motif with cuboidal box as building subunit remains rarely be reported. One of the rational strategies to construct such polycatenated network is the judicious selection of conformationally nonrigid organic
⁎ Corresponding author. Tel.: + 86 591 83711523; fax: + 86 591 83714946. E-mail address: [email protected] (Y.-G. Yao). 1387-7003/$ – see front matter © 2011 Published by Elsevier B.V. doi:10.1016/j.inoche.2011.08.023
ligands since these flexible ligands with appropriate spacers have already proven a certain ability to construct uncommon polycatenation network mainly due to their diverse conformations in the selfassembly process [8]. The mixture of flexible 1,2-bis (4-pyridyl)ethane (bpe) and rigid aromatic carboxylate ligands has been widely used to construct MOFs. Most of them are interpenetrated frameworks [9], but the polycatenated MOFs are still rare. Herein, we describe the reaction of cadmium(II) nitrate, OH-H2BDC and bpe that gives rise to a parallel polycatenation network containing an individual 5-connected bilayer motif [Cd (HO-BDC) (bpe)1.5]n. Moreover, this compound exhibits intense yellow luminescence at room temperature. A mixture of Cd(NO3)2⋅4H2O (0.5 mmol, 0.154 g), HO-H2BDC (0.5 mmol, 0.105 g) and bpe (0.5 mmol, 0.092 g) in 12 ml mixed solvent of H2O and EtOH (V/V=5:1) was stirred for 30 min at room temperature, and then the reaction mixture was sealed in a Teflon-lined reactor and kept at 160 °C for 72 h under autogenous pressure. After being slowly cooled to the room temperature, brown crystals [10] were obtained in 55% yield (based on Cd). Compound 1 was identified by satisfactory elemental analysis, IR spectroscopy (Fig. S7), powder X-ray diffraction and single-crystal X-ray diffraction [11]. Single-crystal X-ray structural analysis shows that compound 1 features a 2D double layer structure with large channels along crystallographic a axis (Fig. S1). The fundamental unit is shown in Fig. 1; there are one crystallographic independent Cd(II) ion, one HO-BDC anion, one and a half bpe ligands. Each Cd(II) ion is seven-coordinated and can be described as a distorted {CdN3O4} pentagonal bipyramid geometry. Two pairs of chelating carboxylate O donors from different HO-BDC ligands and one pyridyl N donor from a bpe ligand comprise the equatorial plane; two pyridyl N donors from another two bpe ligands occupy
2
X. Zhang et al. / Inorganic Chemistry Communications 15 (2012) 1–4
Fig. 1. Coordination environment around Cd(II) ion. All hydrogen atoms attached to carbon atoms were omitted for clarity. Symmetry codes: (A) 1 + x, y, z; (B) x, y, − 1 + z.
the remaining axial sites [N1–Cd1–N2B= 174.425(2)°]. The Cd–O and Cd–N distances are in the range of 2.278(5)–2.667(7) Å and 2.326(4)– 2.385(5) Å, respectively, which are in accordance with Cd(II) polymers previously reported [12]. Interestingly, bpe ligands use their end N donors bridging different Cd(II) ions with the Cd⋅⋅⋅Cd separation of 13.947(5) and 14.010(9) Å, respectively, giving rise to a 1D infinite cationic {[Cd2(bpe)3]4+}n ladder chain propagating along c axis (Fig. 2a). The HO-BDC anions act as chelating bis-bidentate ligands and bridge the neighboring parallel cationic ladder chains into a neutral 2D double layer motif (Fig. 2b). From a topological viewpoint, this 2D double layer motif can be simplified into a (4,5) net by viewing metal centers as nodes and organic spacers as linkers (Fig. 2c). A prominent structural feature of 1 is the existence of cuboidal box of {Cd8(bpe)8(HOip)4} in the double layer structure (Fig. S1). Each cuboidal box consists of eight Cd(II) ions at the corners connected
by eight long bpe ligands and four HO-BDC ligands, which make up the 12 edges of the cuboidal box. The approximate dimension of the cuboidal box is 14.010 × 13.947 × 10.282 Å. Viewing along the a axis, very large regular square channels are evident in the single bilayer motif (Fig. S2). Although large channels exit in the single double layer motif, they are interpenetrated by the identical bilayer motifs. Thus, the most fascinating structural feature of 1 is that each 5-connected 2D double layer motif, which is parallel to each other, is interlocked with the adjacent identical ones. Therefore, the resulting 3D array is an infinite polycatenation of the 2D double layer motif (Fig. 3). The catenation occurs between the bpe ligand and cavum of the cuboidal box (Fig. S3). Although some examples of polycatenated MOFs have been reported [13], to the best of our knowledge, such kind of 2D + 2D → 3D polycatenation of the bilayer motif has not been observed previously in seven-coordinated cadmium(II) polymers. The experimental powder X-ray diffraction (PXRD) pattern of 1 agrees well with the simulated one based on the single-crystal Xray diffraction data (Fig. S4), suggesting that it is in pure phase. To study the stability of the title compound, thermogravimetric analysis (TGA) was performed on a polycrystalline sample of this compound. No obvious weight loss was observed in the temperature range of 30–167 °C. Upon heating above 167 °C, decomposing started and significant weight loss occurred, indicating that the whole framework can be stable up to 167 °C (Fig. S5). The solid-state photoluminescent properties of compound 1 have been investigated at room temperature and the emission and excitation spectra are shown in Fig. 4. It can be observed that intense emission occurred at 542 nm upon excitation of 432 nm for 1 (Fig. S6). In order to ascertain the ascription of the emission band, we referred to many literatures and found that the aromatic dicarboxylate ligand and N, N′bipyridyl ligand are nearly nonfluorescent in the range of 400–600 nm at ambient temperature [9a]. Thus, the emission of 1 may be assigned to the ligand-to-metal-charge-transfer (LMCT). In summary, an interesting luminescent cadmium polymer has been successfully synthesized under hydrothermal conditions. It features a 5connected 2D bilayer motif. Moreover, this 2D bilayer motif is further interlocked with each other, thus generating the final 3D polycatenation array.
Fig. 2. (a) 1D infinite cationic {[Cd2(bpe)3]4+}n ladders along c axis. (b) 2D bilayer motif. (c) Schematic representation of the 5-connected bilayer motif (yellow atoms: Cd centers; purple bonds: HO-BDC ligands; green bonds: bpe ligands).
X. Zhang et al. / Inorganic Chemistry Communications 15 (2012) 1–4
3
Fig. 3. (a) Parallel polycatenation of the 5-connected bilayer motif. (b) Schematic representation of the polycatenated 5-connected bilayer.
Fig. 4. Emission spectrum 1 in the solid-state at room temperature.
Acknowledgements This work was supported by 973 Program of China (2011CBA00505), the Chinese Academy of Sciences (KJCX2-YW-H30, KGCX2-YW-222 and KJCX2-YW-M10) and the Science Foundation of the Fujian Province (2009HZ0005-1 and 2006L2005).
Appendix A. Supplementary data CCDC NO. 802446; contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic data Center Via http://www.ccdc. cam.ac.uk/data_request/cif. TGA and powder X-ray patterns can be found in the supporting file. Supplementary data to this article can be found online at doi:10.1016/j.inoche.2011.08.023.
References [1] (a) B. Moulton, M.J. Zaworotko, From molecules to crystal engineering: supramolecular isomeric and polymorphism in network solids, Chemical Reviews 101 (2001) 1629–1658; (b) O.R. Evans, W.B. Lin, Crystal engineering of NLO materials based on metalorganic coordination networks, Accounts of Chemical Research 35 (2002) 511–522. [2] (a) S. Kitagawa, R. Kitaura, S.I. Noro, Functional porous coordination polymers, Angew Chemie International Edition 43 (2004) 2334–2375; (b) C. Janiak, Engineering coordination polymers towards applications, Dalton Transactions (2003) 2781–2804.
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