کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1313132 975532 2006 10 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Electrolyte effects on the intervalence transition within discrete binuclear cyano-bridged complexes. An estimation of activation free energy from static, optical and electrochemical data
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
Electrolyte effects on the intervalence transition within discrete binuclear cyano-bridged complexes. An estimation of activation free energy from static, optical and electrochemical data
چکیده انگلیسی

A study of the metal-to-metal charge-transfer (MMCT) transition within the binuclear cyano-bridged complexes cis-[L13CoIII(μ-NC)FeII(CN)5]− (L13 = 12-methyl-1,4,7,10-tetraazacyclotridecan-12-amine), trans-[L14CoIII(μ-NC)FeII(CN)5]− (L14 = 6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine) and trans-[L15CoIII(μ-NC)FeII(CN)5]− (L15 = 10-methyl-1,4,8,12-tetraazacyclopentadecan-10-amine) has been carried out in electrolyte solutions at varying concentrations. Using these data, as well as the reaction free energies obtained from electrochemical measurements, the reorganisation and activation free energies for the forward and reverse thermal electron-transfer processes have been estimated. The changes of these parameters with the electrolyte concentration, as well as those of the energy of the maximum MMCT band and the reaction free energy, are mainly due to ion-pairing effects.

Structure and UV-spectrum of the trans-[L14CoIII(μ-CN)FeII(CN)5]− complex. The picture shows experimental (symbols) and simulated (solid lines) data of the characteristic bands for the chromophores CoIII and FeII. The metal to metal charge transfer (MMCT) band is also shown (dashed line). The connection between optical and thermal electron transfer processes allow the estimation of the activation free energy.Figure optionsDownload as PowerPoint slide

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Inorganica Chimica Acta - Volume 359, Issue 1, 1 January 2006, Pages 149–158
نویسندگان
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