Photophysical and Chiroptical Properties of Pyrazino-Phenanthroline-Helicene Derivative and its Rhenium(I) Complex.

IF 3.5 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Chemistry - An Asian Journal Pub Date : 2025-01-21 DOI:10.1002/asia.202401735

Debsouri Kundu, Dominika Jelonek, Natalia Del Rio, Nicolas Vanthuyne, Monika Srebro-Hooper, Jeanne Crassous

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Abstract

A novel coordination motif comprising [4]helicene fused with pyrazino-phenanthroline (H4PP) has been synthesized and reacted with ReCl(CO)₅ to yield its rhenium(I) complex (Re-H4PP). Absorption and emission spectroscopic analysis conducted in dichloromethane and 2-methyltetrahydrofuran reveals that combining pyrazino-phenanthroline with helicene visibly affects the photophysical attributes of both the resulting ligand and its Re(I) complex as compared to their non-helicene analogues, and even more importantly leads to relatively high photoluminescence quantum yield values, especially in the case of H4PP (29 %). Chiroptical studies through electronic circular dichroism and circularly polarized luminescence performed on enantiomerically enriched samples of Re-H4PP show the chiral nature of low-energy excited states affording notable g_lum values that amplify at cryogenic temperatures. Insights into experimental results are provided via first-principles quantum-chemical calculations showing important role of intra-ligand charge-transfer (ILCT) and metal-to-ligand CT (MLCT) states in determining photophysical features of these systems.

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吡嗪-菲罗啉-螺旋烯衍生物及其铼(I)配合物的光物理和热学性质。

合成了一种由[4]螺旋烯与吡嗪-菲罗啉（H4PP）融合组成的新型配位基序，并与ReCl(CO)5反应生成铼(I)配合物（Re-H4PP）。在二氯甲烷和2-甲基四氢呋喃中进行的吸收和发射光谱分析表明，与非螺旋烯类似物相比，吡嗪-菲罗啉与螺旋烯结合明显影响了所得到的配体及其Re(I)配合物的光物理性质，更重要的是导致了相对较高的光致发光量子产率值，特别是在H4PP的情况下（29%）。通过电子圆二色性和圆偏振发光对Re-H4PP的对映体富集样品进行的手性研究表明，低能激发态具有明显的手性性质，在低温下其胶值会放大。通过第一性原理量子化学计算，揭示了配体内部电荷转移（ILCT）和金属-配体（MLCT）态在决定这些系统的光物理特性中的重要作用。

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

Chemistry - An Asian Journal 化学-化学综合

CiteScore

7.00

自引率

2.40%

发文量

535

审稿时长

1.3 months

期刊介绍： Chemistry—An Asian Journal is an international high-impact journal for chemistry in its broadest sense. The journal covers all aspects of chemistry from biochemistry through organic and inorganic chemistry to physical chemistry, including interdisciplinary topics. Chemistry—An Asian Journal publishes Full Papers, Communications, and Focus Reviews. A professional editorial team headed by Dr. Theresa Kueckmann and an Editorial Board (headed by Professor Susumu Kitagawa) ensure the highest quality of the peer-review process, the contents and the production of the journal. Chemistry—An Asian Journal is published on behalf of the Asian Chemical Editorial Society (ACES), an association of numerous Asian chemical societies, and supported by the Gesellschaft Deutscher Chemiker (GDCh, German Chemical Society), ChemPubSoc Europe, and the Federation of Asian Chemical Societies (FACS).