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

doi:10.6023/A13030272

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

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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

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,jplang@suda.edu.cn; 陈阳, chemsunnychan@gmail.com; Tel.: 0512-65882865; Fax: 0512-65880089 E-mail:jplang@suda.edu.cn;chemsunnychan@gmail.com
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 Chunyan^a,b, Chen Yang^a, Li Duanxiu^a, Ren Zhigang^a, Li Hongxi^a, Sun Zhenrong^c, Lang Jianping^a,b

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).

1. 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.PDF(486KB)

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.

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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

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

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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