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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Photophysics and Luminescence Spectroelectrochemistry of [Tc(dmpe)_3]~(+/2+) (dmpe = 1,2-bis(dimethylphosphino)ethane)
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Photophysics and Luminescence Spectroelectrochemistry of [Tc(dmpe)_3]~(+/2+) (dmpe = 1,2-bis(dimethylphosphino)ethane)

机译：[Tc（dmpe）_3]〜（+ / 2+）（dmpe = 1,2-双（二甲基膦基）乙烷）的光物理和发光光谱电化学

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摘要

The ligand-to-metal charge transfer (LMCT) excited state luminescence of [Tc(dmpe)_3]~(2+) (dmpe is 1,2-bis- (dimethylphosphino)ethane) has been measured in solution at room temperature and is compared to its Re analogue. Surprisingly, both [M(dmpe)_3]~(2+)* (M = Re, Tc) species have extremely large excited-state potentials (ESPs) as oxidants, the highest for any simple coordination complex of a transition metal. Furthermore, this potential is available using a photon of visible light (calculated for M = Tc; E~(°′*) = +2.48 V versus SCE; λ_(max) = 585 nm). Open shell time-dependent density functional theory (TDDFT) calculations support the assignment of the lowest energy transition in both the technetium and rhenium complexes to be a doublet?doublet process that involves predominantly LMCT (dmpe-to-metal) character and is in agreement with past assignments for the Re system. As expected for highly oxidizing excited state potentials, quenching is observed for the excited states of both the rhenium and technetium complexes. Stern?Volmer analysis resulted in quenching parameters for both the rhenium and technetium complexes under identical conditions and are compared using Rehm?Weller analysis. Of particular interest is the fact that both benzene and toluene are oxidized by both the Re and Tc systems.
机译：[Tc（dmpe）_3]〜（2 +）（dmpe为1,2-双-（二甲基膦基）乙烷）的配体-金属电荷转移（LMCT）激发态发光已在室温下进行了测量，并且与其Re类似物进行比较。出乎意料的是，[M（dmpe）_3]〜（2 +）*（M = Re，Tc）物质都具有极高的激发态电势（ESPs）作为氧化剂，是过渡金属的任何简单配位络合物中最高的。此外，可以使用可见光的光子获得此电势（计算得出：M = Tc; E〜（°'*）= +2.48 V（相对于SCE;λ_（max）= 585 nm））。开壳时间相关密度泛函理论（TDDFT）计算支持将and和rh络合物中最低的能量跃迁分配为一个双重峰过程，该过程主要涉及LMCT（金属-金属-dpe）特征，并且相符过去为Re系统分配的任务。正如对高氧化态激发态电势的预期，,和tech配合物的激发态均被猝灭。 Stern-Volmer分析得出identical和tech配合物在相同条件下的淬灭参数，并使用Rehm？Weller分析进行比较。特别令人感兴趣的是，苯和甲苯都被Re和Tc系统氧化。

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