Acta Chimica Sinica ›› 2013, Vol. 71 ›› Issue (06): 906-912.DOI: 10.6023/A13030272 Previous Articles     Next Articles


卤离子导向合成配位聚合物[Hg2X4(ppt)]n (X=I和Br; ppt=1-(4-吡啶基)-吡啶铵-4-硫醇盐)及不同的一维链状结构和三阶非线性光学响应

倪春燕a,b, 陈阳a, 李端秀a, 任志刚a, 李红喜a, 孙真荣c, 郎建平a,b   

  1. a 苏州大学材料与化学化工学部 苏州 215123;
    b 中国科学院上海有机化学研究所金属有机化学国家重点实验室 上海 200032;
    c 华东师范大学物理系 上海 200062
  • 投稿日期:2013-03-14 发布日期:2013-05-02
  • 通讯作者: 郎建平,; 陈阳,; Tel.: 0512-65882865; Fax: 0512-65880089;
  • 基金资助:

    项目受国家自然科学基金(No. 21171124)及上海有机化学研究所金属有机化学重点实验室开放基金(No. 201201006)资助.

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 Chunyana,b, Chen Yanga, Li Duanxiua, Ren Zhiganga, Li Hongxia, Sun Zhenrongc, Lang Jianpinga,b   

  1. 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:2013-03-14 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).

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