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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Dual Emission of a Novel (P,N) Re-I Complex: A Computational and Experimental Study on [P,N-{(C6H5)(2)(C5H4N)P}Re(CO)(3)Br]
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Dual Emission of a Novel (P,N) Re-I Complex: A Computational and Experimental Study on [P,N-{(C6H5)(2)(C5H4N)P}Re(CO)(3)Br]

机译：新型（P，N）Re-I络合物的双重发射：[P，N-{（C6H5）（2）（C5H4N）P} Re（CO）（3）Br]的计算和实验研究

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摘要

The spectroscopic, electrochemical, and photophysical properties of the new complex [P,N-{(C6H5)(2)(C5H4N)-P}Re(CO)(3)Br] are reported. The UV-vis spectrum in dichloromethane shows an absorption maximum centered at 315 rim and a shoulder at 350 nm. These absorption bands have been characterized to have MLCT character. Excitation at both wavelengths (maximum and shoulder) leads to an emission band centered at 550 nm. Cyclic voltammetry experiments show two ill-defined irreversible oxidation waves around +1.50 and 1.80 V that are assigned to Re-I/Re-II and Re-II/Re-III couples whereas an irreversible reduction signal centered at 1.80 V is :likewise assigned to a ligand reduction process. These results support the proposal of the MLCT nature of the states implied by the emission of the complex. The luminescent decay fits to a biexponential function, where the lifetimes and emission quantum yields are dependent on the solvent polarity. DFT calculations suggest that d pi -> pi*(pyridine) and d pi -> pi*(phenyl) excited states may account for the existence of two decay lifetimes.
机译：报道了新络合物[P，N-{（C6H5）（2）（C5H4N）-P} Re（CO）（3）Br]的光谱，电化学和光物理性质。二氯甲烷中的UV-vis光谱显示最大吸收位于315边缘，肩部位于350 nm。这些吸收带已经被表征为具有MLCT特性。在两个波长（最大和最大）处的激发都会导致发射带集中在550 nm处。循环伏安法实验表明，在+1.50和1.80 V附近有两个不确定的不可逆氧化波，分别分配给Re-I / Re-II和Re-II / Re-III对，而同样以1.80 V为中心的不可逆还原信号也被分配还原配体的过程。这些结果支持了复合物排放所暗示的国家的MLCT性质的提议。发光衰减符合双指数函数，其中寿命和发射量子产率取决于溶剂极性。 DFT计算表明，d pi-> pi *（吡啶）和d pi-> pi *（苯基）激发态可能解释了两个衰变寿命的存在。

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