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Acta Chimica Sinica >

2013 , Vol. 71 >Issue 06: 906 - 912

DOI: https://doi.org/10.6023/A13030272

Article

Halide-Directed Synthesis of Coordination Polymers [Hg2X4(ppt)]n (X=I and Br, ppt=1-(4-Pyridyl)-pyridinium-4-thiolate) with Different One-Dimensional Chain Structures and Third-Order Nonlinear Optical Properties

  • Ni Chunyan ,
  • Chen Yang ,
  • Li Duanxiu ,
  • Ren Zhigang ,
  • Li Hongxi ,
  • Sun Zhenrong ,
  • Lang Jianping
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  • a College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123;
    b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032;
    c Department of Physics, East China Normal University, Shanghai 200062

Received date: 2013-03-14

  Online published: 2013-05-02

Supported by

Project supported by the National Natural Science Foundation of China (No. 21171124) and the State Key Laboratory of Organometallic Chemistry of Shanghai Institute of Organic Chemistry (No. 201201006).

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Abstract

Solvothermal reactions of HgX2 (X=I, Br) with 4,4'-dipyridyl disulfide (dpds) in acetonitrile gave rise to two one-dimensional polymers [Hg2X4(ppt)]n [ppt=1-(4-pyridyl)-pyridinium-4-thiolate; X=I (1), Br (2)]. In the structures of 1 and 2, the ppt ligand was in situ generated from the Hg(II)-engaged cleavage of both S—S and S—C bonds of dpds and the subsequent rearrangement reactions under solvothermal conditions. Although compounds 1 and 2 have similar chemical formula, 1 crystallizes in the orthorhombic space group Ima2 and holds a 1D non-centrosymmetric zigzag chain while 2 crystallizes in the orthorhombic space group Pnma and has a 1D centrosymmetric zigzag chain. Such a difference in structural symmetry between 1 and 2 may be due to the fact that the radius of iodide is larger than that of bromide. The third-order nonlinear optical (NLO) behaviours of 1 and 2 in DMF were investigated by using femtosecond degenerate four-wave mixing technique. Compound 1 exhibited relatively strong NLO responses while compound 2 showed nothing. Such a remarkable difference in the NLO property may be due to the fact that iodide is a better electron donor than bromide, which allows more efficient spin-orbital coupling, and facilitates intersystem crossing and more efficient usage of triplet excited state absorption.

Key words： halide-directed; coordination polymer; solvothermal synthesis; structure; nonlinear optical properties

Cite this article

Ni Chunyan , Chen Yang , Li Duanxiu , Ren Zhigang , Li Hongxi , Sun Zhenrong , Lang Jianping . Halide-Directed Synthesis of Coordination Polymers [Hg2X4(ppt)]n (X=I and Br, ppt=1-(4-Pyridyl)-pyridinium-4-thiolate) with Different One-Dimensional Chain Structures and Third-Order Nonlinear Optical Properties[J]. Acta Chimica Sinica, 2013 , 71(06) : 906 -912 . DOI: 10.6023/A13030272

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