Structural Variation from 1D to 3D: Effects of Ligands and Solvents on the Construction of Lead(II)-Organic Coordination Polymers

• Published in: Chemistry : a European journal Vol. 13; no. 11; pp. 3248 - 3261
• Main Authors: Yang, Jin, Li, Guo-Dong, Cao, Jun-Jun, Yue, Qi, Li, Guang-Hua, Chen, Jie-Sheng
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.01.2007; WILEY‐VCH Verlag
• Subjects: carboxylate ligands; lead; luminescence; nonlinear optics; supramolecular chemistry
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.200600730

A series of PbII coordination polymers [Pb(ndc)(dpp)] (1), [Pb(ndc)(ptcp)]⋅0.5 H2O (2), [Pb(ndc)(dppz)] (3), [Pb(ndc)(tcpn)2] (4), [Pb2(ndc)2(tcpp)] (5), [Pb(Hndc)2]⋅H2O (6), [Pb(ndc)(dma)] (7), [Pb(bdc)(dma)] (8), [Pb(trans‐chdc)(H2O)] (9), and [Pb2(cis‐chdc)2]⋅NH(CH3)2 (10), where ndc=1,4‐naphthalenedicarboxylate, dpp=4,7‐diphenyl‐1,10‐phenanthroline, ptcp=2‐phenyl‐1H‐1,3,7,8‐tetraazacyclopenta[l]phenanthrene, dppz=dipyrido[3,2‐a:2′,3′‐c]phenazine, tcpn=2‐(1H‐1,3,7,8‐tetraazacyclopenta[l]phenanthren‐2‐yl)naphthol, tcpp=4‐(1H‐1,3,7,8‐tetraazacyclopenta[l]phenanthren‐2‐yl)phenol, dma=N,N‐dimethylacetamide, bdc=1,4‐benzenedicarboxylate, and chdc=1,4‐cyclohexanedicarboxylate, have been synthesized from a hydrothermal or solvothermal reaction system by varying the ligands or the solvents. Compounds 1–5 crystallize with an N‐donor chelating ligand and an aromatic dicarboxylate linker. Compounds 1–4 are 1D polymers with different π–π stacking interactions, whereas compound 5 consists of 2D layers. The structures of compounds 7, 8, and 10 are 3D frameworks formed by connection of the PbII centers by organic acid ligands. Compound 7 is chiral although the ndc ligand is achiral, while the framework of 8 is a typical 3D (3,4)‐connected net. Compound 10 is the first example of PbII wheel cluster [Pb8O8] units bridged by carboxylate groups. Compound 6 contains 1D chains which are further extended to a 3D structure by π–π interactions. Compound 9 consists of a 2D network constructed by PbII centers and trans‐chdc ligands. The structural differences between 7 and 8 and between 9 and 10 indicate the importance of solvents for framework formation of the coordination polymers. By varying the solvent the cis and trans conformations of H2chdc in 9 and 10 were separated completely. The photoluminescence and nonlinear optical properties of the coordination polymers have also been investigated. Wide structural variety ranging from 1D chains to 2D layers to 3D frameworks (see picture for some examples) is exhibited by a series of PbII coordination polymers obtained by hydro(solvo)thermal synthesis with different dicarboxylate ligands, N‐donor chelating ligands, and solvents. The photoluminescence and nonlinear optical properties of the compounds were also investigated.