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首页> 外文期刊>Chemistry: A European journal >A Heteroleptic Ferrous Complex with Mesoionic Bis(1,2,3-triazol-5-ylidene) Ligands: Taming the MLCT Excited State of Iron(II)
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A Heteroleptic Ferrous Complex with Mesoionic Bis(1,2,3-triazol-5-ylidene) Ligands: Taming the MLCT Excited State of Iron(II)

机译：具有介电双（1,2,3-三唑-5亚基）配体的亚铁配合物：驯化MLCT激发态的铁（II）

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摘要

Strongly sigma-donating N-heterocyclic carbenes (NHCs) have revived research interest in the catalytic chemistry of iron, and are now also starting to bring the photochemistry and photophysics of this abundant element into a new era. In this work, a heteroleptic Fe-II complex (1) was synthesized based on sequentially furnishing the Fe-II center with the benchmark 2,2-bipyridine (bpy) ligand and the more strongly sigma-donating mesoionic ligand, 4,4-bis(1,2,3-triazol-5-ylidene) (btz). Complex1 was comprehensively characterized by electrochemistry, static and ultrafast spectroscopy, and quantum chemical calculations and compared to [Fe(bpy)(3)](PF6)(2) and (TBA)(2)[Fe(bpy)(CN)(4)]. Heteroleptic complex1 extends the absorption spectrum towards longer wavelengths compared to a previously synthesized homoleptic Fe-II NHC complex. The combination of the mesoionic nature of btz and the heteroleptic structure effectively destabilizes the metal-centered (MC) states relative to the triplet metal-to-ligand charge transfer ((MLCT)-M-3) state in 1, rendering it a lifetime of 13ps, the longest to date of a photochemically stable Fe-II complex. Deactivation of the (MLCT)-M-3 state is proposed to proceed via the (MC)-M-3 state that strongly couples with the singlet ground state.
机译：强烈贡献σ的N-杂环卡宾（NHC）引起了人们对铁催化化学的研究兴趣，并且现在也开始将这种丰富元素的光化学和光物理学带入一个新时代。在这项工作中，在依次为Fe-II中心提供基准2,2-联吡啶（bpy）配体和更强σ供体的中性离子配体4,4-的基础上，合成了一种杂配Fe-II复合物（1）。双（1,2,3-三唑-5-亚烷基）（btz）。复合物1通过电化学，静态和超快速光谱学以及量子化学计算进行了全面表征，并与[Fe（bpy）（3）] [PF6] [2）和（TBA] [2] [Fe（bpy）（CN）（ 4）]。与以前合成的均相Fe-II NHC复合物相比，异相复合物1将吸收光谱扩展到更长的波长。相对于1中的三重态金属-配体电荷转移（（MLCT）-M-3）状态，btz的中离子性质和杂配结构的组合有效地破坏了以金属为中心的（MC）状态的稳定性13ps，是迄今为止光化学稳定的Fe-II络合物中最长的。建议通过（MC）-M-3状态与单线基态强耦合进行（MLCT）-M-3状态的停用。

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