Formation of Infinite Linear Mercury Metal Chains Assisted by Face-to-Face pi-pi (Aryl-Aryl) Stacking Interactions

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Title:	Formation of Infinite Linear Mercury Metal Chains Assisted by Face-to-Face pi-pi (Aryl-Aryl) Stacking Interactions
Authors:	Wu, JY (Wu, Jing-Yun) Hsu, HY (Hsu, Hung-Yu) Chan, CC (Chan, Chun-Chieh) Wen, YS (Wen, Yuh-Sheng) Tsai, C (Tsai, Chiitang) Lu, KL (Lu, Kuang-Lieh)
Contributors:	化學系
Keywords:	CENTER-DOT-CL COORDINATION POLYMERS HYDROGEN-BONDS LUMINESCENT PROPERTIES CRYSTAL-STRUCTURES GOLD(I) COMPLEXES CARBENE COMPLEXES HALIDE-COMPLEXES SELF-ASSOCIATION MOLECULAR WIRES
Date:	2009-01
Issue Date:	2011-12-09 15:15:23 (UTC+8)
Abstract:	Polymeric mercury compounds, [HgCl(2)(bpym)](n) (1, bpym = 5,5'-bipyrimidine), [Hg(2)Br(4)(bpym)](n) (2), and [HgX(2)(bpyz)](n) (3-Cl, X = Cl; 3-Br, X = Br; bpyz = 2,2'-bipyrazine), which are composed of linear mercury chains were assembled from HgX(2) (X = Cl, Br) and either 5,5'-bipyrimidine or 2,2'-bipyrazine at ambient temperature. Single-crystal X-ray diffraction analysis revealed that 1 presents a two-dimensional layer structure involved with one-dimensional linear mercury chains at a mercurophilic distance of 3.77 angstrom. It is linked by bridging chlorides and stabilized by weak, slipped face-to-face, pi-pi (aryl-aryl) interactions between the coordinated bpym ligands. These layers are interdigitated-stacked into a three-dimensional supramolecular architecture through C-H center dot center dot center dot N and C-H center dot center dot center dot Cl-Hg hydrogen bonding interactions. Compound 2 has a two-dimensional (4,4) layer structure comprised of four-connected bpym nodes and linear Br-Hg-Br linkers. The layers are stagger-stacked in a three-dimensional supramolecular network, thereby forming zigzag mercury chains with a Hg center dot center dot center dot Hg separation of 3.94 angstrom and a Hg center dot center dot center dot Hg center dot center dot center dot Hg angle of 110 degrees. Compounds 3-Cl and 3-Br are isostructural and supported by powder X-ray diffraction (PXRD) data. Crystallographical analysis showed that compound 3-Br adopts a two-dimensional (4,4) layer architecture with linear mercury chains comprised of two types of interlaced Hg(bpyz) and HgBr(2) chains. Within the linear mercury chains, the Hg atoms separate at a long distance of 4.01 angstrom. The bpyz ligand is bridged to two Hg(II) centers with its two exo-N-donors in an anti-conformation and has a dihedral angle of 0 degrees between the two hinged pyrazine rings. It is interesting to note that halide alone is not sufficient to induce linearity and face-to-face pi-pi (aryl-aryl) interactions between the coordinated organic ligands are the primary influence in the formation of linear mercury chains in 1, 3-Cl, and 3-Br.
Appears in Collections:	[Department of Chemistry & Graduate Institute of Applied Chemistry ] journal articles

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