富地球金属配合物的 LMCT 和 MLCT 激发态的氧化还原反应性

IF 1.7 4区 化学
Wonwoo Nam, Yong-Min Lee, Shunichi Fukuzumi
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引用次数: 0

摘要

贵金属络合物是一种出色的光氧化催化剂,现在已被富土金属络合物所取代。本综述重点研究了富土金属配合物的配体-金属电荷转移(LMCT)和金属-配体电荷转移(MLCT)激发态的氧化还原反应性。具有强σ捐献型 NHC 配体(NHC = N-heterocyclic carbene)的铁络合物已经出现,由于通过金属中心态去活化的障碍显著增加,这些铁络合物具有长寿命的 LMCT 激发态。铁(III)-NHC 复合物是各种光催化氧化还原反应的有效光氧化催化剂。虽然锰(IV)-氧配合物没有长寿命激发态(τ < < 1 ns)。一旦酸(如 Sc(OTf)3 和 HOTf)与锰(IV)-氧配合物的氧原子结合,酸结合锰(IV)-氧配合物的光激发就会形成微秒寿命的激发态,这些激发态能够将包括苯在内的底物氧化成苯酚。锰(III)、锰(II)和锰(I)配合物的光激发态可作为光还原剂还原包括 O2 在内的底物。另一方面,Co(IV) 和 Co(III) 复合物的光激发态起光氧化剂的作用,而 Co(II) 和 Co(I) 复合物的光激发态则起光还原剂的作用。在激发态寿命方面,[Cr(tpe)2]3+(tpe = 1,1,1-三(吡啶-2-基)乙烷)的发光寿命最长(τ = 4500 μs),是光催化氧化还原反应的有效光氧化催化剂。Cr(0) 复合物的 LMCT 状态是一种超级光还原剂。因此,富土金属配合物的 LMCT 和 MLCT 激发态可分别用作强光氧化剂和光还原剂。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Redox reactivity of LMCT and MLCT excited states of Earth-abundant metal complexes

Redox reactivity of LMCT and MLCT excited states of Earth-abundant metal complexes

Precious metal complexes, which act as excellent photoredox catalysts, have now being replaced by earth-abundant metal complexes. This review focused on redox reactivity of ligand-to-metal charge transfer (LMCT) and metal-to-ligand charge transfer (MLCT) excited states of earth-abundant metal complexes. Iron complexes with strongly σ-donating NHC-ligands (NHC = N-heterocyclic carbene) has emerged, featuring long lived LMCT excited states due to a significantly increased barrier for deactivation via metal centered states. A Fe(III)-NHC complex acts as an effective photoredox catalyst for various photocatalytic redox reactions. Although manganese(IV)-oxo complexes have no long-lived excited states (τ < < 1 ns). Once acids such as Sc(OTf)3 and HOTf are bound to the oxo moiety of Mn(IV)-oxo complexes, the photoexcitation of acid-bound Mn(IV)-oxo complexes resulted in formation of the excited states with microseconds lifetimes, which are capable of oxidation of substrates including benzene to phenol. Photoexcited states of Mn(III), Mn(II) and Mn(I) complexes act as photoreductants to reduce substrates including O2. On the other hand, photoexcited states of Co(IV) and Co(III) complexes act as photooxidants, whereas those of Co(II) and Co(I) complexes act as photoreductants. With regard to the excited state lifetime, [Cr(tpe)2]3+ (tpe = 1,1,1-tris(pyrid-2-yl)ethane) exhibited the longest luminescence lifetime (τ = 4500 μs), acting as an effective photoredox catalyst for photocatalytic redox reactions. The LMCT state of a Cr(0) complex acts as a super photoreductant. Thus, LMCT and MLCT excited states of earth-abundant metal complexes are utilized as strong photooxidants and photoreductants, respectively.

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来源期刊
Bulletin of the Korean Chemical Society
Bulletin of the Korean Chemical Society Chemistry-General Chemistry
自引率
23.50%
发文量
182
期刊介绍: The Bulletin of the Korean Chemical Society is an official research journal of the Korean Chemical Society. It was founded in 1980 and reaches out to the chemical community worldwide. It is strictly peer-reviewed and welcomes Accounts, Communications, Articles, and Notes written in English. The scope of the journal covers all major areas of chemistry: analytical chemistry, electrochemistry, industrial chemistry, inorganic chemistry, life-science chemistry, macromolecular chemistry, organic synthesis, non-synthetic organic chemistry, physical chemistry, and materials chemistry.
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