- 期刊
具氧化還原活性之二茂鐵分子導線
Redox-Active Ferrocenyl-Ethynyl Group Containing Molecular Wires
摘要
探討一系列具有typ-(fc)_n-typ, typ-C≡C-(fc)_n-C≡C-typ[(η^5-C_5H_5)(P_2)M^(II)-C≡C-(fc)_n-C≡C-M^(II)(P_2)(η^5-C_5H_5)], [(η^5-C_5H_(10))(P_2)M^)(II)-C≡C-(fc)_n-C≡C-M^(II)(P_2)(η^5-C_5H_(10))], (typ = terpyridine, fc = ferrocenyl; M = Fe(II),Ru(II), Os(II); P_2 = Ph_2PCH_2CH_2PPh_2 (dppe)或(PPh_3)_2)分子式的一系列分子導線，從單晶結構、電化學行為、光學數據比較其導電特性。這些化合物在無水二氯甲烷中相對於Ag/AgCl參考電極，在0.0到1.0 V間可以進行連續的氧化還原反應，且低電位之氧化還原波是來自於兩末端金屬的貢獻。透過電化學技術測量末端金屬間的E_(1/2)及第二氧化還原電位，可以估計兩末端金屬間電子偶合作用力的大小，根據實驗結果得知二茂鐵-乙炔基可以在兩金屬中心間，提供快速定量的資訊移轉，所以是個前途大有可為的橋接基團。
並列摘要
The single crystal structures, electrochemical, and spectral properties of a series of multinuclear ferrocenyl complexes with formula typ-(fc)_n-typ, typ-C≡C-(fc)_n-C≡C-typ [(η^5- C_5H_5)(P_2)M^(II)-C≡C-(fc)_n-C≡C-M^(II)(P_2)(η^5-C_5H_5)], [(η^5-C_5H_(10))(P_2)M^(II)-C≡C-(fc)_n-C≡C-M^(II)(P_2)(η^5- C_5H_(10))], (typ = terpyridine, fc = ferrocenyl; M = Fe(II), Ru(II), Os(II); P_2 = Ph_2PCH_2CH_2PPh_2 (dppe) or (PPh_3)_2) have been discussed. These complexes undergo sequential reversible oxidation events from 0.0 to 1.0 V referred to the Ag/AgCl electrode in anhydrous CH_2Cl_2 solution and the low-potential waves have been assigned to be the two end-capped metallic centers. The magnitude of the electronic coupling between the two terminal metallic centers in the series of complexes was estimated by the electrochemical technique. Based on the correlation between the ΔE_(1/2) values and the second redox potentials of the end-capping metallic centers in the series of complexes, a qualitative explanation for the difference of the electronic coupling is given. Electrochemical measurements indicate that ferrocenyl-ethynyl spacers appear to be promising spacers which can ensure fast and quantitative transfer of information between two metal centers.