A Core-Shell Spectroscopic Perspective on Solution Phase Charge Transfer in Photoexcited Push-Pull Chromophores

IF 8.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science Pub Date : 2026-10-15 DOI:10.1039/d6sc06430b

Mate Kurucz,Marc-Oliver Winghart,Debkumar Rana,Victoria Kabanova,Jibrael Rolston,Martha Yaghoubi Jouybari,Mattis Fondell,Sebastian Eckert,Philippe Wernet,Albert Stolow,Arnaud Rouzee,Michael S. Schuurman,Erik T. J. Nibbering

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引用次数: 0

Abstract

Push-pull chromophores typically have a D-π-A molecular architecture with an electron-rich donor group D and an electron-poor acceptor group A, linked by aromatic π units. Here, we demonstrate using the prototypical push-pull chromophore 4-(dimethylamino)benzonitrile (DMABN) in solvents of varying polarity, that time-resolved soft X-ray absorption spectroscopy (XAS) combined with state-of-the-art ab initio quantum chemical simulation, provides quantitative insight into how changes in frontier molecular orbital interactions determine the charge-transfer properties of the molecule. Exploiting the element-specific sensitivity of XAS, we characterize the electronic structures of the locally excited and charge-transfer states within the first singlet excited-state manifold and, in addition, unambiguously identify the early-time population of a triplet state. Our results suggest a common underlying mechanism governing the charge redistribution and population dynamics of the excited electronic states in DMABN, with implications for controlling the photophysical properties of push-pull chromophores in charge-transfer applications.

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光激发推拉发色团中溶液相电荷转移的核壳光谱研究

推拉发色团具有典型的D-π-A分子结构，具有富电子的给体基团D和电子贫乏的受体基团a，由芳香π单元连接。在这里，我们展示了在不同极性的溶剂中使用典型的推拉发色团4-（二甲氨基）苯腈（DMABN），时间分辨软x射线吸收光谱（XAS）与最先进的从头算量子化学模拟相结合，为前沿分子轨道相互作用的变化如何决定分子的电荷转移性质提供了定量的见解。利用XAS的元素特异性灵敏度，我们表征了第一个单线态激发态流形中的局部激发态和电荷转移态的电子结构，此外，明确地识别了三重态的早期居群。我们的研究结果提示了DMABN中控制电荷再分配和激发态居群动力学的共同潜在机制，这对控制电荷转移应用中推拉发色团的光物理性质具有重要意义。

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

Chemical Science CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

4.80%

发文量

1352

审稿时长

2.1 months

期刊介绍： Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.