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光介导下,一种具有双齿喹喔啉配体的三羰基锰(Ⅰ)配合物释放一氧化碳。

Light-mediated CO release from a tricarbonyl manganese(i) complex with a bidentate quinoxaline ligand.

作者信息

Khaled Rabaa M, Radacki Krzysztof, Mostafa Gamal A E, Ali Essam A, Shehab Ola R, Mansour Ahmed M

机构信息

Department of Chemistry, Faculty of Science, Cairo University Gamma Street Giza 12613 Egypt

Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg Am Hubland D-97074 Würzburg Germany.

出版信息

RSC Adv. 2025 Aug 12;15(35):28642-28650. doi: 10.1039/d5ra03678j. eCollection 2025 Aug 11.

Abstract

Reaction between 2-(pyridin-2-yl)quinoxaline (L) and [MnBr(CO)] afforded a dark-stable -[MnBr(CO)L] that releases CO upon exposure to visible light (468-525 nm). Different structural elucidation methods, including X-ray crystallography, were used to thoroughly characterize the structure of the organometallic compound. Prior to recording the profiles of dark-stability and photolysis in various organic solvents, the complex's solvatochromism features were examined experimentally and through quantum chemical calculations. As solutions become less polar, the lowest energy transition in DMSO, which is observed at 487 nm, is red-shifted, which could be explained by negative solvatochromism. Illuminating the pre-incubated solutions of the complex in organic solvents at 525 nm, with or without calf-thymus DNA, hen white egg lysozyme, or histidine, yields a two-step process perhaps associated with the sequential release of 3 CO molecules. In comparison, the principal factor influencing the CO release kinetics of the complex is the medium and the percentage of DMSO for example, with minimal interference from the biomolecules.

摘要

2-(吡啶-2-基)喹喔啉(L)与[MnBr(CO)]反应生成了一种在黑暗中稳定的-[MnBr(CO)L],该化合物在可见光(468 - 525 nm)照射下会释放出CO。使用了包括X射线晶体学在内的不同结构解析方法对该有机金属化合物的结构进行了全面表征。在记录该配合物在各种有机溶剂中的黑暗稳定性和光解曲线之前,通过实验和量子化学计算研究了该配合物的溶剂化显色特性。随着溶液极性降低,在DMSO中于487 nm处观察到的最低能量跃迁发生红移,这可以用负溶剂化显色来解释。在525 nm波长下,用或不用小牛胸腺DNA、蛋清溶菌酶或组氨酸照射该配合物在有机溶剂中的预孵育溶液,会产生一个可能与3个CO分子的顺序释放相关的两步过程。相比之下,影响该配合物CO释放动力学的主要因素是介质以及DMSO的百分比,例如,生物分子的干扰最小。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bad2/12376878/b71930d7f2c1/d5ra03678j-s1.jpg

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