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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Electronic Structures of 9,10-Anthrylene Dimers and Trimers in Solution: Formation of Charge Separation States Depending on Alkyl Substituent Groups
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Electronic Structures of 9,10-Anthrylene Dimers and Trimers in Solution: Formation of Charge Separation States Depending on Alkyl Substituent Groups

机译：溶液中9,10-蒽二聚体和三聚体的电子结构：取决于烷基取代基的电荷分离态的形成

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摘要

Electronic structures of 9,10-anthrylene dimers and trimers analogous to 9,9'-bianthryl (BA) have been investigated by means of steady-state fluorescence and transient absorption spectroscopy and dipole moment evaluation based on the solvatochromic fluorescence shifts and integrated electrooptical emission measurements (IEOEM) in various solvents. Formation of the charge-separation (CS) state in the excited state was strongly dependent on the substituent group: unsubstituted and n-hexyl-substituted anthrylenes exhibited almost same behavior compared to BA, whereas the tert-butyl-substituted dimer and trimer relaxed into an excitonic state rather than the CS state even in a polar solvent. The lower possibility of the CS state for the tert-butyl-substituted anthrylenes was mainly ascribed to the smaller solvation energy because of the larger effective Onsager cavity due to bulky tert-butyl groups. The limitation of a simple continuum model using Onsager's reaction field was also discussed in relation to the solvent-induced electronic structure change in the excited state of anthrylenes.
机译：通过稳态荧光和瞬态吸收光谱以及基于溶剂变色荧光位移和集成电光发射的偶极矩评估，研究了类似于9,9'-双蒽（BA）的9,10-蒽二聚体和三聚体的电子结构在各种溶剂中进行测量（IEOEM）。处于激发态的电荷分离（CS）状态的形成很大程度上取决于取代基：与BA相比，未取代的和正己基取代的蒽表现出几乎相同的行为，而叔丁基取代的二聚体和三聚体则松弛成甚至在极性溶剂中也能产生激子态而不是CS态。叔丁基取代的蒽的CS态较低的可能性主要归因于较小的溶剂化能，这是由于庞大的叔丁基导致的更大的Onsager空穴所致。还讨论了使用Onsager反应场的简单连续谱模型的局限性，与在蒽的激发态下溶剂诱导的电子结构变化有关。

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