Influence of Iodine Substitutions on the Photophysical Properties of Rhenium(I) Tricarbonyl Complexes With Pyridine Schiff Base (PSB-IHB)

IF 2.3 3区化学 Q3 CHEMISTRY, PHYSICAL

International Journal of Quantum Chemistry Pub Date : 2025-01-08 DOI:10.1002/qua.70005

Rosaly Morales-Guevara, Dayán Páez-Hernández, Evys Ancede-Gallardo, Alexander Carreño

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Abstract

This theoretical investigation aims to evaluate the influence of iodine substitutions on the phenolic moiety of the pyridine Schiff bases harboring an intramolecular hydrogen bond (PSB-IHB) ancillary ligand within the monocationic. fac-[Re(CO)₃(N,N)(PSB-IHB)]⁺ architecture on photophysical properties, particularly emission range. Optimized structures of two Re(I) tricarbonyl complexes (C1 and C2) were analyzed, revealing a distorted octahedral coordination geometry. Geometric parameters were compared with experimental data from analogous complexes. NBO analysis confirmed the presence of intramolecular hydrogen bonds (IHBs) in both singlet and triplet states, providing significant stabilization. Theoretical calculations predicted three distinct absorption bands for all complexes in dichloromethane, indicating substantial electronic delocalization between the pyridinic and phenolic rings via the azomethine group. These findings underscore the crucial role of delocalization and donor–acceptor interactions in stabilizing Re(I) tricarbonyl complexes and their impact on photophysical properties. Emissions calculated for the C1 and C2 complexes were observed within the range of 632–643 nm. The presence of IHBs was found to be essential for modulating photophysical properties, with emissions attributed to ligand-to-ligand charge transfer transitions.

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碘取代对吡啶席夫碱铼(I)三羰基配合物（PSB-IHB）光物理性质的影响

本理论研究旨在评价碘取代对单阳离子中含有分子内氢键（PSB-IHB）辅助配体的吡啶席夫碱的酚类部分的影响。face -[Re(CO)3(N，N)(PSB-IHB)]+结构对光物理性质，特别是发射范围的影响。对两种Re(I)三羰基配合物（C1和C2）的优化结构进行了分析，显示出畸变的八面体配位几何。将几何参数与类似复合体的实验数据进行了比较。NBO分析证实了分子内氢键（IHBs）在单线态和三重态的存在，提供了显著的稳定性。理论计算预测了二氯甲烷中所有配合物的三个不同的吸收带，表明吡啶环和酚环之间通过亚甲基进行了大量的电子离域。这些发现强调了离域和供体-受体相互作用在稳定Re(I)三羰基配合物及其对光物理性质的影响中的关键作用。计算的C1和C2配合物的辐射在632-643 nm范围内。发现ihb的存在对于调节光物理性质是必不可少的，其发射归因于配体到配体的电荷转移跃迁。

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

International Journal of Quantum Chemistry 化学-数学跨学科应用

CiteScore

4.70

自引率

4.50%

发文量

185

审稿时长

2 months

期刊介绍： Since its first formulation quantum chemistry has provided the conceptual and terminological framework necessary to understand atoms, molecules and the condensed matter. Over the past decades synergistic advances in the methodological developments, software and hardware have transformed quantum chemistry in a truly interdisciplinary science that has expanded beyond its traditional core of molecular sciences to fields as diverse as chemistry and catalysis, biophysics, nanotechnology and material science.