中文摘要：

通过HgX2 （X=I, Br）与4,4＇-二吡啶基二硫化物（dpds）在乙腈中的溶剂热反应, 得到二个含1-（4-吡啶基）-吡啶铵-4-硫醇盐（ppt）的一维配位聚合物： [Hg2I4（ppt）]n （1）和[Hg2Br4（ppt）]n （2）. 在化合物1和2结构中ppt配体是由dpds在溶剂热反应条件下通过dpds的S—S键和S—C键切断然后进行重排在原位形成的. 化合物1具有非中心对称的一维Z字型链状结构, 化合物2则具有中心对称的一维Z字型链状结构. 用飞秒简并四波混频法测定了1和2溶液的三阶非线性光学性质, 化合物1具有较强的非线性光学响应, 而化合物2却没有非线性光学响应, 这种性质的差异可能由于碘离子是较溴离子更好的电子授体, 化合物1有较小的HOMO-LUMO能级, 更易发生电子在体系间跃迁, 更有效使用三线激发态吸收.

英文摘要：

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.