A Red‐Light‐Driven CO‐Releasing Complex: Photoreactivities and Excited‐State Dynamics of Highly Distorted Tricarbonyl Rhenium Phthalocyanines
A Red‐Light‐Driven CO‐Releasing Complex: Photoreactivities and Excited‐State Dynamics of Highly Distorted Tricarbonyl Rhenium Phthalocyanines
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红光驱动的CO释放复合物：高度畸变三羰基铼酞菁的光反应性和激发态动力学
DOI：
10.1002/chem.202200716
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Ishii Kazuyuki
中科院分区：
文献类型：
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作者：
Wang Mengfei;Murata Kei;Koike Yosuke;Jonusauskas Gediminas;Furet Amaury;Bassani Dario M.;Saito Daisuke;Kato Masako;Shimoda Yuushi;Miyata Kiyoshi;Onda Ken;Ishii Kazuyuki
由一个[Re(CO)3]+单元和一个酞菁(Pc)配体(Re1Pc)组成的配合物在红光照射下，在O2和配位溶剂的存在下，作为光诱导CO释放分子(PhotoCORM)发挥作用，可以深入穿透活组织。瞬时吸收光谱测量表明，含有两个[Re(CO)3]+单元的Re1Pc和Re2Pc具有很短的激发态寿命和超快的系间交叉。激发态的性质归因于有效的自旋-轨道耦合和大的Frank-Condon因子，源于配合物的扭曲结构，即[Re(CO)3]+单元(S)的不对称配位，其中之一通过对具有两个[Re(CO)3]+单元的对称取代的Pc的单晶X射线分析得到证实。Re1Pc代表了一种很有前途的红光驱动光CORM，可以应用于生物环境或治疗应用。
A complex comprising one [Re(CO)3] + unit and a phthalocyanine (Pc) ligand (Re1Pc) is shown to function as a photoinduced CO-releasing molecule (photoCORM) in the presence of O2 and a coordinative solvent under irradiation with red light, which can deeply penetrate living tissues. Transient absorption spectroscopic measurements indicate very short excited-state lifetimes and ultrafast intersystem crossing for Re1Pc and Re2Pc, which contains two [Re(CO)3] + units. The excited-state properties are ascribed to efficient spin-orbit coupling and large Franck-Condon factors originating from the complexes' distorted structures, i.e., unsymmetric coordination of [Re(CO)3] + unit(s), one of which was confirmed via single-crystal Xray analysis of a symmetrically-substituted Pc with two [Re(CO)3] + units. Re1Pc represents a promising red light-driven photoCORM that can be applied in biological environments or therapeutic applications.