Abstract
The synthesis of poly(ether)tailed bipyridine complex as redox reaction probes has advanced attempts to interpret very slow diffusion and heterogeneous electron transfer. Diffusion coefficients as low as $1.5{\times}10^{-15}cm^2/s$ have been observed for the oxidation of neat $Co(bpy(ppgm)_2)_{3^-}(ClO_4)_2$ with $LiClO_4$ electrolyte. Heterogeneous electron transfer rate constants of materials were found to vary with diffusion coefficient. The decrease in k as the diffusion coefficient decreases was actually caused by the decreasing D. Diffusion coefficient for compound of strong ion pairing anion($ClO{_4}^-$) was much smaller than the diffusion coefficient for compound of weak ion pairing anion($CF_3COO^-$).
산화환원반응 탐침제로, poly ether 꼬리가 결합된 Cobalt(II)bipyridine 착물을 합성 하였고, 이들 화합물의 느린 확산계수와 불균일 전자이동을 설명하였다. $Co(bpy(ppgm)_2)_{3^-}(ClO_4)_2$에 전해질 $LiClO_4$가 혼합된 neat 상태의 산화반응에 대한 확산계수는 $1.5{\times}10^{-15}cm^2/s$ 였다. 이 화합물들의 불균일 전자이동 속도상수들은 확산계수와 관련이 있었다. 확산계수의 감소에 따라 속도상수(k)의 감소가 일어났다. 강한 이온쌍을 형성하는 $ClO{_4}^-$의 화합물은 약한 이온 쌍을 형성하는 $CF_3COO^-$ 화합물보다 확산계수가 훨씬 작았다.