Characterization of redox states of Ru(OH(2))(Q)(tpy)(2+) (Q = 3,5-di-tert-butyl-1,2-benzoquinone, tpy = 2,2':6',2''-terpyridine) and related species through experimental and theoretical studies.
Characterization of redox states of Ru(OH(2))(Q)(tpy)(2+) (Q = 3,5-di-tert-butyl-1,2-benzoquinone, tpy = 2,2':6',2''-terpyridine) and related species through experimental and theoretical studies.
复制标题
Ru(OH(2))(Q)(tpy)(2 ) 氧化还原态的表征（Q = 3,5-二叔丁基-1,2-苯醌，tpy = 2,2:6，
作者：
Ming;J. Rochford;Dmitry E. Polyansky;Tohru Wada;Koji Tanaka;E. Fujita;J. Muckerman
通过实验和理论UV-Vis光谱和Pourbai图研究了Ru(OH(2))(Q)(Tpy)(2+)(q=3，5-二叔丁基-1，2-苯二酚，tpy=2，2‘：6’，2‘-联吡啶)的氧化还原态。报道了在水溶液中由去质子化和氧化还原过程产生的物种的电化学性质。用电子结构理论系统地指认了各种中间络合物中氧化还原对的形式氧化态。通过从头算方法和破缺对称密度泛函理论(DFT)方法的比较，研究了铁磁与反铁磁耦合的电子归属问题。计算了包括质子耦合电子转移(PCET)过程在内的各种pK(A)值和还原电势，并构造了Pourbai x图的理论版本，以阐明和指认实验图中几个先前不明确的区域。
The redox states of Ru(OH(2))(Q)(tpy)(2+) (Q = 3,5-di-tert-butyl-1,2-benzoquinone, tpy = 2,2':6',2''-terpyridine) are investigated through experimental and theoretical UV-vis spectra and Pourbaix diagrams. The electrochemical properties are reported for the species resulting from deprotonation and redox processes in aqueous solution. The formal oxidation states of the redox couples in the various intermediate complexes are systematically assigned using electronic structure theory. The controversy over the electronic assignment of ferromagnetic vs. antiferromagnetic coupling is investigated through comparison of ab initio methods and the broken-symmetry density functional theory (DFT) approach. The various pK(a) values and reduction potentials, including the consideration of proton-coupled electron-transfer (PCET) processes, are calculated, and the theoretical version of the Pourbaix diagram is constructed in order to elucidate and assign several previously ambiguous regions in the experimental diagram.