TUNABLE ELECTRON-DENSITY AT A RHENIUM CARBONYL COMPLEX COORDINATED TO THE CONDUCTING POLYMER POLY[5,5'-(2-THIENYL)-2,2'-BITHIAZOLE]

被引:105
作者
WOLF, MO [1 ]
WRIGHTON, MS [1 ]
机构
[1] MIT,DEPT CHEM,CAMBRIDGE,MA 02139
关键词
D O I
10.1021/cm00045a009
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The synthesis of a conducting polymer by electropolymerization of 5,5'-(2-thienyl)-2,2'-bithiazole is reported. Films of this polymer exhibit electrochemical behavior typical of conducting polymers and have a conductivity of approximately 0.2 OMEGA-1 cm-1 at 25-degrees-C in 0.1 M [n-Bu4N]PF6/CH2Cl2 at the potential of maximum conductivity (approximately +1.5 V vs Ag). The activation energy for conductivity for partially oxidized (approximately +1.3 V vs Ag) films is 0.25 Ev. Reaction of these polymer films with refluxing solutions of Re(CO)5Cl in CHCl3 yields polymers in which the [Re(CO)3Cl] moiety is bound to the bithiazolyl sites in the polymer. Subsequent reaction with AgPF6 converts the Re centers to cationic [Re(CO)3(CH3CN)]+ groups. These polymers were characterized by XPS and surface reflectance FTIR. The polymer containing the cationic Re groups is conducting (approximately 2 x 10(-3) OMEGA-1 cm-1 at +1.5 V vs Ag). The potential region in which the polymer is conducting does not overlap with any Re-centered oxidations, but oxidation of films of the polymer to the conducting state causes electron density to be removed from the Re center, resulting in a shift of the carbonyl stretching frequencies to higher energy. At the potential of maximum conductivity this shift is 4-6 cm-1.
引用
收藏
页码:1526 / 1533
页数:8
相关论文
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