物理化学学报 >> 2010, Vol. 26 >> Issue (08): 2158-2162.doi: 10.3866/PKU.WHXB20100822

电化学 上一篇    下一篇

含电子给体乙炔二茂铁化合物的光谱及电化学性质

曹迁永1, 卢 鑫1, 匡仁云2, 李志华1, 杨震宇1   

  1. 1. 南昌大学化学系, 南昌 330031;
    2. 井冈山大学化学化工学院, 江西 吉安 343009
  • 收稿日期:2010-01-05 修回日期:2010-04-06 发布日期:2010-07-23
  • 通讯作者: 曹迁永 E-mail:cqyong@ncu.edu.cn
  • 基金资助:

    国家自然科学基金(20963007), 江西省教育厅自然科学基金(GJJ09074)和南昌大学创新团队基金资助

Optical and Electrochemical Properties of Ethynyl-Bridged Ferrocenes with Electron Donor Groups

CAO Qian-Yong1, LU Xin1, KUANG Ren-Yun2, LI Zhi-Hua1, YANG Zhen-Yu1   

  1. 1. Department of Chemistry, Nanchang University, Nanchang 330031, P. R. China;
    2. College of Chemistry and Chemical Engineering, Jinggangshan University, Ji'an 343009, Jiangxi Province, P. R. China
  • Received:2010-01-05 Revised:2010-04-06 Published:2010-07-23
  • Contact: CAO Qian-Yong E-mail:cqyong@ncu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20963007), Bureau of Education of Jiangxi Province, China (GJJ09074) and Program for Innovative Research Team of Nanchang University, China.

摘要:

合成了三种含电子给体乙炔基桥连二茂铁化合物Fc—C≡C—Ph—(p-OMe)(3a), Fc—C≡C—Ph—(p-NMe2)(3b)与Fc—C≡C—Ph—(p-NPh2)(3c), 并对其结构、光化学及电化学性质进行了表征. 吸收光谱表明, 所有化合物在可见光区400-550 nm都可归属为Fe(II)Cp—C≡C—Ph—(p-R)(Cp为环戊二烯基)的金属到配体的电荷跃迁(MLCT)光谱, 同时检测到3a与3c氧化态在近红外区(分别位于946与1044 nm)可归属为Cp—C≡C—Ph—(p-R)Fe(III)的配体到金属的电荷跃迁(LMCT). 电化学测试结果表明, 三种化合物都有稳定的Fc+/Fc可逆氧化还原电位, 且3b与3c还出现Ph—NR2的氧化电位. 3b对质子表现出光及电化学敏感性, 随着质子的加入, 其MLCT光谱红移, Fc+/Fc电位正移, 而Ph—NR+2/ Ph—NR2峰消失.

关键词: 二茂铁, 质子化, 吸收光谱, 氧化, 电化学

Abstract:

We present the synthesis, optical and electrochemical properties of three ethynyl-bridged ferrocenes with electron donor groups, Fc—C≡C—Ph-(p-OMe) (3a), Fc—C≡C—Ph-(p-NMe2) (3b) and Fc—C≡C—Ph—(p-NPh2) (3c). All three compounds show a Fe(II)Cp—C≡C—Ph—(p-R) (Cp=cyclopentadienyl) metal to ligand charge transition (MLCT) in 400-550 nm. Upon oxidation, 3a and 3c show a Cp—C≡C—Ph—(p-R)Fe(III) ligand to metal charge transition (LMCT) in the near-IR range (946 and 1044 nm). A reversible Fc+/Fc potential for 3a-3c and an irreversible Ph—NR+2/Ph—NR2 potential for 3b and 3c are observed by in the cyclic and differential pulse voltammetry. Finally, 3b shows an optical and electrochemical response upon protonation, with a red shift of the MLCT transition, an anodic shift of the Fc+/Fc potential, and disappearance of the Ph—NR+2/Ph—NR2 peak.

Key words: Ferrocene, Protonation, Absorption spectrum, Oxidation, Electrochemistry

MSC2000: 

  • O646