Modulating the Charge Transfer Coupling in Boron-Dipyrromethene Homodimers by π-Bridge Units.

IF 2.8 2区 化学 Q3 CHEMISTRY, PHYSICAL
The Journal of Physical Chemistry B Pub Date : 2025-04-03 Epub Date: 2025-03-19 DOI:10.1021/acs.jpcb.5c00292
Li Ma, Zhuoran Kuang, Hao Zhang, Yan Wan, Yuanyuan Guo, Andong Xia, Yang Li
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引用次数: 0

Abstract

To mimic the excitation energy conversion mechanisms observed in natural light-harvesting systems, we have extensively investigated photoinduced symmetry-breaking charge separations (SBCSs) in various multichromophoric model systems have been extensively investigated. However, designing multichromophoric model systems capable of simultaneously achieving ultrafast and complete SBCS remains a significant challenge. In this study, we employed benzene, thiophene, and furan as π-bridges to develop a series of boron dipyrromethene (BODIPY) homodimers. Spectral analysis, together with an estimation of the π-bridge-dependent charge transfer (CT) coupling using the fragment charge difference method, reveals that π-bridge units with different electron-donating abilities can effectively modulate the CT coupling between chromophores. Notably, the furan-based π-bridge, exhibiting the most pronounced electron-donating character, facilitates symmetry-breaking charge transfer (SBCT), i.e., excimer formation with a time constant of about 12 ps in weak polar toluene. Furthermore, a dramatic increase in the SBCS rate constant was observed in highly polar acetonitrile, improving from 60.4 ps for the benzene-bridged homodimer to 2.9 ps for the furan-bridged counterpart. These findings underscore the potential of π-bridge units in tuning the photophysical properties of covalent molecular aggregates by optimizing such systems for specific applications such as organic photovoltaics and photocatalysis.

用π桥单元调制硼-二吡咯甲烷同型二聚体中的电荷转移耦合。
为了模拟在自然光收集系统中观察到的激发能转换机制,我们广泛地研究了各种多色模型系统中的光致对称破缺电荷分离(SBCSs)。然而,设计能够同时实现超快和完整SBCS的多色模型系统仍然是一个重大挑战。本研究以苯、噻吩和呋喃为π桥,制备了一系列硼二吡咯烯(BODIPY)同型二聚体。光谱分析和碎片电荷差法对π桥相关电荷转移耦合的估计表明,具有不同给电子能力的π桥单元可以有效地调节发色团之间的CT耦合。值得注意的是,呋喃基π桥具有最明显的供电子特性,有利于弱极性甲苯中对称破断电荷转移(SBCT),即以约12 ps的时间常数形成准分子。此外,在高极性乙腈中观察到SBCS速率常数的显著增加,从苯桥接的同型二聚体的60.4 ps提高到呋喃桥接的2.9 ps。这些发现强调了π桥单元在调整共价分子聚集体的光物理性质方面的潜力,通过优化这些系统用于有机光伏和光催化等特定应用。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
CiteScore
5.80
自引率
9.10%
发文量
965
审稿时长
1.6 months
期刊介绍: An essential criterion for acceptance of research articles in the journal is that they provide new physical insight. Please refer to the New Physical Insights virtual issue on what constitutes new physical insight. Manuscripts that are essentially reporting data or applications of data are, in general, not suitable for publication in JPC B.
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