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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Electro-and photochemical properties of a(mu-alkoxo)bis(mu-carboxylato)diruthenium complex having two tetraphenylporphinato zinc(II)moieties
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Electro-and photochemical properties of a(mu-alkoxo)bis(mu-carboxylato)diruthenium complex having two tetraphenylporphinato zinc(II)moieties

机译：具有两个四苯基卟啉锌（II）部分的（μ-烷氧基）双（μ-羧基羧基）二钌配合物的电和光化学性质

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摘要

The novel(mu-alkoxo)bis(mu-carboxylato)diruthenium complex K[Ru_2(dhpta)(mu-O_2C-p)-ZnTPP)_2] 3 was prepared by simple ligand substitution reaction.Strong antiferromagnetic interaction between two Ru~(III)ions of 3 was observed with a coupling constant of-425-404 cm~(-1).The cyclic voltammogram of 3 can be explained in terms of superposition of those of ZnTPP-p-CO_2H and K[Ru_2(dhpta)(mu-O_2CPh)_2] 2,indicating no significant electrochemical interaction.The large conproportionation constant estimated from the reduction potentials for Ru~(III)Ru~(III)and Ru~(III)Ru~(III)indicates great stability of the mixed-valence state.The mixed-valence species [Ru~(III)Ru~(III)(dhpta)(mu-O_2C-p-ZnTPP)_2]_2~ 4 was prepared by controlled potential electrolysis.The electronic absorption spectrum of 4 was quite similar to that of [Ru~(III)Ru~(III)(dhpta)(mu-O_2CCH_3)_2]_2-which is a typical Class II complex.The fluorescence from the S_2 state of the ZnTPP unit of 3 was significantly(78%)quenched.The electron transfer from the ZnTPP unit to Ru~(III)ions in 3 is a plausible mechanism,even though energy transfer could not be ruled out completely.The free energy change for electron transfer,DELTAG_(CS),was estimated to be ca.-1.1 eV,which is similar to typical values for the reorganization energy gamma in polar solvents.Hence,the electron transfer scheme is situated almost at the top of the Marcus parabola,enabling ultrafast electron transfer.
机译：通过简单的配体取代反应制备了新型的（mu-alkoxo）双（mu-羧基）二钌络合物K [Ru_2（dhpta）（mu-O_2C-p）-ZnTPP）_2]3。两个Ru〜（之间的强反铁磁相互作用观察到3的离子具有耦合常数-425-404 cm〜（-1）.3的循环伏安图可以用ZnTPP-p-CO_2H和K [Ru_2（dhpta）的叠加表示（mu-O_2CPh）_2] 2，表明没有明显的电化学相互作用。根据Ru〜（III）Ru〜（III）和Ru〜（III）Ru〜（III）的还原电势估算的大配比常数表明其稳定通过控制电位电解制备了混合价态[Ru〜（III）Ru〜（III）（dhpta）（mu-O_2C-p-ZnTPP）_2] _2〜4。电子吸收光谱4的值与[Ru〜（III）Ru〜（III）（dhpta）（mu-O_2CCH_3）_2] _2相似，后者是典型的II类络合物.ZnTPP单元的S_2状态发出的荧光3被显着（78％）淬灭。尽管无法完全排除能量转移，但从ZnTPP单元向Ru〜（III）离子的ctron转移是一个合理的机制。据估计，电子转移的自由能变化DELTAG_（CS）约为。 -1.1 eV，与极性溶剂中重组能γ的典型值相似。因此，电子转移方案几乎位于抛物线的顶部，可实现超快电子转移。

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