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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Excited State Characterization of Carborane-Containing Poly(dihexyl fluorene)s
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Excited State Characterization of Carborane-Containing Poly(dihexyl fluorene)s

机译：含碳碳聚（二己基芴）S的激发状态表征

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摘要

Carborane-containing poly(dihexylfluorene)s experience drastic solvatochromism in both the solution and solid states, a characteristic that is advantageous for use in environmental and biological sensing applications. Understanding the intrinsic decay mechanisms that give rise to such sensitive emission properties is important for designing responsive sensors. The solution-state photophysical properties of homopolymer, poly(9,9-dihexyl-(bisfluorenyl)carborane) (PFCY), and alternating copolymer, poly(9,9-dihexy1-2,7-fluorene-alt-9,9-dihexyl(bisfluoreny1)-carborane) (PFCS), were deciphered using steady-state, electrochemical, spectroelectrochemical, and time-resolved spectroscopic methods. From these techniques, it was discovered that following excitation the conjugated fluorene local excited state (LES) donates an electron to the carborane molecule, forming an intramolecular charge transfer (ICT) state between a radical cation on the fluorene moiety and a radical anion on the carborane moiety. From the global analysis of transient absorption data, it was discovered that the rate of electron transfer from the fluorene to the carborane is heavily influenced by solvent polarity and is significantly faster in more polar solvents. Once formed, the ICT state can decay through radiative or nonradiative mechanisms and is more likely to undergo radiative decay in nonpolar solvents, due to an intramolecular restriction of the polar ICT state. This study elucidates the effects that polarity has on the excited-state formation and subsequent decay mechanisms of fluorene-carborane systems, conclusively explaining the solvatochromism and steadystate emission properties exhibited by this system.
机译：含碳氧烷的聚（二己基氟烯）S体验溶液和固态中的激烈溶解度，这是用于环境和生物传感应用的有利性的特性。了解产生这种敏感排放性能的内在衰减机制对于设计响应传感器是重要的。均聚物，聚（9,9-二己基（双芴）碳硼烷）（PFCY），和交替共聚物，聚溶液状态的光物理特性（9,9- dihexy1-2,7芴 - 交替 - 9,9-使用稳态，电化学，光谱电化学和时间分辨光谱方法来破译二己基（Bisfluoreny1） - 羰基）（PFC）。从这些技术中发现，在激发之后，缀合的芴局部激发态（LES）将电子给碳硼烷分子捐赠给电子，在芴部分的自由基阳离子之间形成分子内电荷转移（ICT）状态和基团的阴离子碳钢植物部分。从全局分析瞬态吸收数据，发现从芴与碳硼的电子转移速率受到溶剂极性的严重影响，在更极性的溶剂中明显更快。一旦形成，由于极性ICT状态的分子内限制，ICT状态可以通过辐射或非辐射机制衰减，并且更可能在非极性溶剂中进行辐射衰减。该研究阐明了效应极性对激发态的形成和芴碳硼烷系统的随后衰变机制，决定性说明由该系统表现出的溶剂化和稳态发光特性。

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