五氰鐵四氨釕雙核錯合物trans-[(isn)(NH3)4Ru(4-NCpy)Fe(CN)5]-藉由等當量trans-[Ru(NH3)4(isn)(4-NCpy)]2+ 與[Fe(CN)5(NH3)]3-在pH5水溶液中直接混合而得。trans-[(isn)(NH3)4Ru(4-NCpy)Fe(CN)5]混價雙核錯合物則是將trans-[(isn)(NH3)4Ru(4-NCpy)Fe(CN)5]-溶液以一當量S2O82- 氧化而得。我們從UV-vis光譜、紅外線光譜及電化學結果均顯示混價分子屬定域性Ru(II)、Fe(III)氧化狀態。動力學結果顯示雙核分子trans-[(isn)(NH3)4Ru(4-NCpy)Fe(CN)5]-氧化第一個電子時氧化中心在Ru(II)，形成Ru(III)、Fe(II)氧化態，再經由inner-sphere electron transfer形成穩定的Ru(II)、Fe(III)狀態的混價分子。Hush理論分析價間光譜(intervalence IT band)的結果進一步求得非定域性參數α2= 2 x10-3證實本實驗混價分子屬於定域性結構。 The binuclear complex trans-[(isn)(NH3)4Ru(4-NCpy)Fe(CN)5]- was prepared by mixing equimolar of trans-[Ru(NH3)4(isn)(4-NCpy)]2+ and [Fe(CN)5NH3]3- at pH=5 aqueous solution. The mixed valence complex trans-[(isn)(NH3)4Ru(4-NCpy)Fe(CN)5] was obtained by oxidation of trans-[(isn)(NH3)4Ru(4-NCpy)Fe(CN)5]- with one equivalent of peroxy disulfate. The results of UV-vis, infrared and electrochemical studies all suggested that the mixed valence species featured valence-trapped localized system with Ru(II)、Fe(III) oxidation states. The cyclic voltammogram of binuclear complexes exhibited two electron reversible steps at E1/2 =0.519V and 0.847V (vs. NHE). Which correspond to [III, II] + e- [II, II] and [III, III] +e- [III, II], respectively. The mixed valence complex shows an intervalence band at λmax＝830 nm (1.02×103M-1cm-1). The properties of the IT band conform with Hush’s theory.
