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Photochemical properties of phthalocyanines with transition metal ions
Coordination Chemistry Reviews ( IF 20.3 ) Pub Date : 2022-05-30 , DOI: 10.1016/j.ccr.2022.214626
Mengfei Wang , Kazuyuki Ishii

This review focuses on phthalocyanine (Pc) complexes with transition metal ions, especially the second- and third-row transition metal ions, and summarizes their photochemistry in terms of spin-allowed singlet–singlet (S0-S1) absorption, spin-forbidden singlet–triplet (S0-Tn) absorption, excited-state dynamics, and photofunctions. Characteristic photophysical and photochemical properties are identified from numerous data based on relevant theories. Firstly, it is demonstrated that the Q absorption bands show a blue or red shift with/without broadening owing to the interactions with transition metal ions, which is explained by the energy relationship among the d, π, and π* orbitals. Secondly, it is shown that the Tn energies can be determined based on the strong spin–orbit coupling of transition metal ions: the T1 energy can be evaluated by observing spin-forbidden singlet–triplet (S0-Tn) absorption, whereas the T2 energy of low-symmetry Pc complexes can be determined by analyzing zero-field splitting. Thirdly, numerous data on the excited-state dynamics are summarized and discussed in terms of spin-forbidden processes, such as phosphorescence decay rate and intersystem crossing. Finally, some attractive photofunctions are introduced. To provide a systematic understanding of the roles of the transition metal ions in relation to the characteristic photophysical and photochemical properties of Pcs, brief analyses are provided. This review provides direction for designing various photofunctions based on metal Pc complexes.



中文翻译:

过渡金属离子酞菁的光化学性质

本综述着重于酞菁 (Pc) 与过渡金属离子的配合物,尤其是第二排和第三排过渡金属离子,并从自旋允许的单线态-单线态 (S 0 -S 1 ) 吸收、自旋-禁止单重态-三重态 (S 0 -T n ) 吸收、激发态动力学和光函数。基于相关理论,从大量数据中确定了特征光物理和光化学性质。首先,证明了由于与过渡金属离子的相互作用,Q吸收带显示出蓝移或红移,有/没有变宽,这可以通过d、π和π*轨道之间的能量关系来解释。其次,证明了 T n能量可以基于过渡金属离子的强自旋轨道耦合来确定:T 1能量可以通过观察自旋禁止的单线态-三线态 (S 0 -T n ) 吸收来评估,而 T 2低对称 Pc 配合物的能量可以通过分析零场分裂来确定。第三,根据自旋禁止过程,例如磷光衰减率和系统间交叉,总结和讨论了有关激发态动力学的大量数据。最后,介绍了一些有吸引力的光功能。为了系统地了解过渡金属离子与 Pcs 的特征光物理和光化学性质相关的作用,提供了简要分析。该综述为设计基于金属 Pc 配合物的各种光功能提供了方向。

更新日期:2022-06-03
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