ELECTROPOLYMERIZATION OF BIS(4-CYANO-1-PYRIDINIO) DERIVATIVES FOR THE PREPARATION OF POLYVIOLOGEN FILMS ON ELECTRODES
ELECTROPOLYMERIZATION OF BIS(4-CYANO-1-PYRIDINIO) DERIVATIVES FOR THE PREPARATION OF POLYVIOLOGEN FILMS ON ELECTRODES
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DOI：
10.1246/bcsj.66.2054
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发表时间：
1993-07-01
影响因子：
4
通讯作者：
SHIMIDZU, T
中科院分区：
文献类型：
--
作者：
SAIKA, T;IYODA, T;SHIMIDZU, T
在碱性条件下，用阴极电聚合法合成了6个双(4-氰基-1-吡啶)衍生物(E(Red)=-0.64~-0.74V vs.SCE)。沉积的薄膜是由聚紫精构成的，显示出无色或略黄至蓝或红紫色的特征电致变色。该衍生物被还原为4-氰基-1，4-二氢-4-吡啶自由基，然后依次偶联在电极上形成聚紫精薄膜，从而消除了氰离子。该电聚合方法制备的聚紫精薄膜不溶于水和一般有机溶剂，具有自发交联性。特别是，聚阴离子作为支持电解质，迫使聚紫精在原位形成聚电解质络合物。聚阴离子电解液的表面覆盖电流效率(典型情况下为23%)大约是单体阴离子电解液的四倍。
Six bis(4-cyano-1-pyridinio) derivatives have been synthesized and deposited onto electrodes by cathodic electropolymerization (E(Red) = -0.64--0.74 V vs. SCE) under basic conditions. The deposited films were constructed of polyviologens that showed characteristic electrochromisms with colorless or slightly yellow to blue- or red-violet. The derivative was reduced to 4-cyano-1,4-dihydro-4-pyridyl radicals, which were coupled successively to form a polyviologen film on the electrode with an elimination of cyanide ions. Characteristically, the polyviologen films deposited by this electropolymerization were insoluble in water and common organic solvents with a spontaneous cross-linking. Especially, a polyanion as a supporting electrolyte forced the polyviologen to form a polyelectrolyte complex in situ. The current efficiency of surface coverage with the polyanion electrolyte (23% in the typical case) was about four-times larger than those with monomeric anions.