卤代苯溶剂对镓咔咯配合物光物理性质的影响:外重原子效应

利用紫外-可见光谱、稳态和时间分辨荧光光谱以及飞秒瞬态吸收光谱探测了不同卤代苯溶剂对三种五氟苯基取代的镓咔咯(1-Ga、2-Ga、3-Ga)光物理性质的影响,结果表明卤代苯溶剂的色散力对于镓咔咯电子光谱吸收峰位置的影响起着主要作用;溶剂外重原子效应能显著降低镓咔咯的荧光量子产率。飞秒瞬态吸收光谱表明,光激发下,镓咔咯与卤代苯溶剂之间可发生电子转移反应,溶剂的重原子效应可以减缓电荷分离态复合物电荷重组速率。     

Corrole‐based photodynamic antitumor therapy

Study of photodynamic therapy (PDT) based on corroles has become one of the most important topics in corrole chemistry. Advances in synthetic methodology have made it possible for the preparation of structurally diverse corrole photosensitizers. This review covers the recent progress in the study of corrole as a photosensitizer in the photodynamic antitumor therapy. The content is organized in three sections: cellular uptaking and localization of corrole in tumor cells; morphological changes and cytotoxicity after corrole PDT treatment; and the animal level corrole PDT test. The possible mechanism of corrole‐based PDT antitumor activity is also summarized.     

Cobalt(III) corrole-tethered semiconducting graphdiyne film for efficient electrocatalysis of oxygen reduction reaction

Inspired from nature, transition metal porphyrins and corroles have been designed and synthesized for electrocatalytic oxygen reduction reaction (ORR). However, the efficiency is limited by their low conductivity and thus carbonization is usually required. Herein, we report a new strategy by covalently linking cobalt(III) corrole and cobalt(II) porphyrin onto a semiconducting fluoro-graphdiyne (F-GDY) film through nucleophilic substitution reaction. The crystalline F-GDY film was prepared by Glaser-Hay coupling at the water/dichloromethane interface, followed by ultrasonic-assisted exfoliation in liquid. The Co(III) corrole-tethered F-GDY material exhibited excellent four-electron ORR activity, with a half-wave potential of 0.875 V (vs reversible hydrogen electrode). It also displayed high discharge performance and capacity in a zinc-air battery device, superior to the commercial Pt/C. Our study provides a pyrolysis-free approach toward biomimetic catalysts for efficient small molecule activation.     

Effect of Selective CF3 Substitution on the Physical and Chemical Properties of Gold Corroles

Gold corroles are not readily accessible and they display no interesting physical or chemical properties. A facile methodology has now been developed for obtaining selectively CF₃‐substituted gold(III) corroles and the introduction of these groups has been found to have an immense effect on the structures of the complexes, their photophysical and redox properties, and on their ability to participate in catalytic processes.     

质子化corroles的结构和电子光谱的密度泛函理论研究

用电子密度泛函理论研究了N-质子化corrole(H₄Cor⁺)和meso位芳基取代质子化corroles(H₄TPC⁺、H₄TpFPC⁺和H₄TdCPC⁺)的几何构型、内消旋反应机理以及电子光谱. 结果表明,这些化合物均有两种稳定构型(势能面极小),一个为C₂对称性的S1(最稳定构型),另一为C₁对称性的S2,其中S1的能量比S2低约15.8～18.5 kJ/mol.S1和S2的corrole环都呈现明显的面外扭曲变形. 手性S1的两个对映异构体之间的转化是一个以S2为中间态的多步过程. 用TDDFT计算了它们的紫外可见电子吸收光谱和圆二色谱(ECD). 与H₄Cor⁺相比,H₄TPC⁺、H₄TpFPC⁺和H₄TdCPC⁺的紫外可见吸收都发生了明显红移,且它们的Q带都因芳基取代基与corrole环之间的π-π共轭而明显增强. 计算表明,质子化corrole的若干相邻电子跃迁的旋转强度符号相反,表明ECD谱可能是研究其电子跃迁的有用工具.