物理化学学报 >> 1985, Vol. 1 >> Issue (02): 162-168.doi: 10.3866/PKU.WHXB19850207

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导电高聚物的EXAFS 研究(Ⅰ)铂氯酸(H2PtCl6·6H2O)掺杂的聚乙炔

白春礼; 傅亨; 唐有祺; 曹镛; 钱人元; 陆坤权; 赵雅琴; 常龙存   

  1. 中国科学院化学所晶体结构实验室; 中国科学院化学所有机固体研究室; 中国科学院物理所
  • 收稿日期:1984-08-08 修回日期:1984-12-21 发布日期:1985-04-15

EXAFS STUDY ON ELECTRICALLY CONDUCTIVE POLYMERS(Ⅰ)H2PtCl6·6H2O-DOPED POLYACETYLENE

Bai Chunli; Fu Heng; Tang Youqi; Cao Yong; Qian Renyuan; Lu Kunquan; Zhao Yaqin; Chang Longchun   

  1. Laboratory of Crystal Structure, Institute of Chemistry, Academia Sinica; Laboratory of Organic Solids, Institute of Chemistry, Academia Sinica; Institute of Physics, Academia Sinica
  • Received:1984-08-08 Revised:1984-12-21 Published:1985-04-15

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摘要： 在实验室EXAFS装置上测量了一种导电高聚物——H_2PtCl_6·6H_2O掺杂聚乙炔和模型化合物(K_2PtCl_6)的PtL_Ⅲ吸收谱。用高功率的施转阳极靶X射线发生器(RigakuRU-1000)作为X射线源。观测到的EXAFS数据分析表明, Pt原子在试样中有两种配位状态。一种是PtCl_6~(2-)离子, Pt—Cl键长为0.233 nm, 另一种是Pt在0.228 nm附近有两个最近邻的Cl原子。实验结果提供了支持下述观点的直接结构信息: 随着电子从(CH)_x链向铂盐的转移, 发生下列反应:
2H_2PtCl_6+2e~-→PtCl_6~(2-)+PtCl_2+4HCl

Abstract: PtL_Ⅲ absorption spectra of an electrically conductive polymer——H_2PtCl_6· 6H_2O-doped polyacetylene and the model compound K_2PtCl_6 were measured with a laboratory EXAFS system, which utilizes a high power rotating-anode X-ray gene- rator (Rigaku model RU-1000) as an X-ray source.The Fourier transforms of k~3-weighted EXAFS oscillations of sample and thc model compound are shown in Fig.3. The prominent peak in the Fourier transform for H_2PtCl_6·6H_2O-doped polyaeetylene can be attributed to the Cl atoms surrounding Pt atom. The curvefitting analysis for the first shell shows two types of neighboring Cl atoms with Pt-Cl distances of 0.2329 nm and 0.2277 nm, respectively.
According to the results from use of the theoretical and empircal methods, it is concluded that the dopant anion in polyacetylene film is PtCl_6~(2-). The result provides a direct structural information that supports the proposition: the following reaction accompanied by electron transfer from (CH)_x chains to platinum salt:
2H_2PtCl_6+2e~-→PtCl_6~(2-)+PtCl_2+4HCl