光功能铁配合物激发态调控的研究进展  

Advances in modulation of the excited states of photofunctional iron complexes

作　　者：潘庆君 龚忠亮[1] 钟羽武[1,2] PAN Qingjun;GONG Zhongliang;ZHONG Yuwu(Beijing National Laboratory for Molecular Sciences,CAS Key Laboratory of Photochemistry,CAS Research/Education Center for Excellence in Molecular Sciences,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,China;School of Chemical Sciences,University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]北京分子科学国家研究中心,中国科学院化学研究所,光化学重点实验室,分子科学科教融合卓越创新中心,北京100190 [2]中国科学院大学化学科学学院,北京100049

出　　处：《无机化学学报》2025年第1期45-58,共14页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21925112,22090021,22305251)资助。

摘　　要：许多具有d^(6)和d^(8)电子构型的第二和第三周期过渡金属配合物具有长寿命的金属中心到配体的电荷转移(MLCT)激发态,表现出优异的光化学和光物理性能。然而,这类金属普遍昂贵且在地壳中的丰度很低。因此,开发新型廉价和丰产第一周期过渡金属光功能配合物具有重要的理论研究意义和实际应用价值。其中,具有3d^(6)电子构型的Fe(Ⅱ)和3d^(5)电子构型的Fe(Ⅲ)光功能配合物引起了众多关注。其主要挑战为通过有效的配体设计调控Fe(Ⅱ)配合物的MLCT激发态,以及实现Fe(Ⅲ)配合物配体到金属的电荷转移(LMCT)激发态发光。近年来,相关研究取得了突破性的进展,具有较长MLCT激发态寿命的Fe(Ⅱ)配合物和LMCT发光的Fe(Ⅲ)配合物被陆续开发出来,并成功应用于光化学领域。在此,我们从配合物和配体设计出发,总结了Fe(Ⅱ)和Fe(Ⅲ)配合物激发态调控的最新进展。此外,我们还讨论了Fe(Ⅱ)/Fe(Ⅲ)配合物在光化学领域的潜在应用。Many second and third‑row transition‑metal complexes with d^(6)and d^(8)electronic configurations possess long‑lived metal‑to‑ligand charge‑transfer(MLCT)excited states,endowing them with excellent photochemical and photophysical properties.However,these metals are typically expensive and have a low abundance in the earth's crust.Therefore,it is significant to develop inexpensive and high earth‑abundant first‑row transition‑metal complexes as new photo‑functional materials.Among them,Fe(Ⅱ)complexes with a 3d^(6)electronic configuration and Fe(Ⅲ)complexes with a 3d^(5)electronic configuration are the subject of particular interest.The main challenges are to modulate the MLCT excited state of Fe(Ⅱ)complexes through efficient ligand design and to achieve the ligand‑to‑metal charge transfer(LMCT)luminescence of Fe(Ⅲ)complexes.In recent years,significant progress were made in the studies of Fe(Ⅱ)complexes with relatively long MLCT excited‑state lifetimes and Fe(Ⅲ)complexes with efficient LMCT luminescence.These complexes have been successfully applied in different aspects of photochemistry.This review summarizes the recent advances in modulating the excited‑state properties of photofunctional Fe(Ⅱ)and Fe(Ⅲ)complexes,focusing on the molecular designs of metal complexes and ligands.In addition,the potential developments and applications in the photochemistry of Fe(Ⅱ)/Fe(Ⅲ)complexes are discussed.

关 键 词：丰产金属 铁配合物 配体设计 激发态调控 

分 类 号：O641.4[理学—物理化学]