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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Ultrafast Structural Dynamics of Cu(I)-Bicinchoninic Acid and Their Implications for Solar Energy Applications
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Ultrafast Structural Dynamics of Cu(I)-Bicinchoninic Acid and Their Implications for Solar Energy Applications

机译：Cu（I）-比辛可宁酸的超快结构动力学及其对太阳能应用的启示

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In this study, ultrafast optical transient absorption and X-ray transient absorption (XTA) spectroscopy are used to probe the excited-state dynamics and structural evolution of copper(I) bicinchoninic acid ([Cu(I)- (BCA)_2]~+), which has similar but less frequently studied biquinoline-based ligands compared to phenanthroline-based complexes. The optical transient absorption measurements performed on the complex in a series of polar protic solvents demonstrate a strong solvent dependency for the excited lifetime, which ranges from approximately 40 ps in water to over 300 ps in 2- methoxyethanol. The XTA experiments showed a reduction of the prominent 1s → 4p_z edge peak in the excited-state X-ray absorption nearedge structure (XANES) spectrum, which is indicative of an interaction with a fifth ligand, most likely the solvent. Analysis of the extended X-ray absorption fine structure (EXAFS) spectrum shows a shortening of the metal?ligand bond in the excited state and an increase in the coordination number for the Cu(II) metal center. A flattened structure is supported by DFT calculations that show that the system relaxes into a flattened geometry with a lowest-energy triplet state that has a dipole-forbidden transition to the ground state. While the short excited-state lifetime relative to previously studied Cu(I) diimine complexes could be attributed to this dark triplet state, the strong solvent dependency and the reduction of the 1s → 4p_z peak in the XTA data suggest that solvent interaction could also play a role. This detailed study of the dynamics in different solvents provides guidance for modulating excited-state pathways and lifetimes through structural factors such as solvent accessibility to fulfill the excited-state property requirements for efficient light harvesting and electron injection.
机译：在这项研究中，超快速光学瞬态吸收和X射线瞬态吸收（XTA）光谱被用来探测激发态动力学和二辛可宁酸铜[[Cu（I）-（BCA）_2]〜 +），与基于菲咯啉的配合物相比，具有相似但研究较少的基于联喹啉的配体。在一系列极性质子溶剂中对复合物进行的光学瞬态吸收测量结果表明，该溶剂对激发寿命的依赖性很强，其范围从水中约40 ps到2-甲氧基乙醇中超过300 ps。 XTA实验表明，在激发态X射线吸收近边缘结构（XANES）光谱中，突出的1s→4p_z边缘峰减少，这表明与第五种配体（最可能是溶剂）的相互作用。对扩展的X射线吸收精细结构（EXAFS）光谱的分析表明，在激发态下金属配体键的缩短和对Cu（II）金属中心的配位数的增加。 DFT计算支持扁平结构，该DFT计算表明系统松弛到具有最低能量三重态的扁平几何形状，该三态态具有禁止偶极跃迁到基态的状态。虽然相对于先前研究的Cu（I）二亚胺络合物而言，激发态寿命短可归因于这种暗三重态，但XTA数据中强烈的溶剂依赖性和1s→4p_z峰的减少表明溶剂相互作用也可以发挥作用职务。这项对不同溶剂动力学的详细研究为通过结构因素（例如溶剂可及性）来调节激发态途径和寿命提供了指导，从而满足有效收集光和电子注入的激发态特性要求。

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