Visible Light Absorption and Long-Lived Excited States in Dinuclear Silver(I) Complexes with Redox-Active Ligands
Visible Light Absorption and Long-Lived Excited States in Dinuclear Silver(I) Complexes with Redox-Active Ligands
复制标题
具有氧化还原活性配体的双核银 (I) 配合物的可见光吸收和长寿命激发态
DOI：
10.1021/acs.inorgchem.0c02938
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发表时间：
2020
影响因子：
4.6
通讯作者：
Campbell, Michael G.
中科院分区：
文献类型：
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作者：
Shields, Dylan J.;Elkoush, Tasneem;Miura-Stempel, Emily;Mak, Choi L.;Niu, Guang-Hao;Gudmundsdottir, Anna D.;Campbell, Michael G.
定义良好的双核银(I)配合物已成为催化和材料化学应用的目标，银-银密切相互作用对电子结构的影响仍然是一个积极探索的领域。在这项研究中，我们描述了具有氧化还原活性的萘嘧啶二亚胺配体的二聚银配合物的合成、结构和光物理性质。与银(I)不同的是，这些配合物在可见光区显示出吸收特征，这是由于金属-金属到配体的电荷转移（MMLCT）跃迁，这是由银-银密切相互作用和低配体π*轨道的结合引起的。通过光谱和计算相结合的研究探索了配合物的光物理性质，揭示了MMLCT激发态寿命超过1 μs。这些结果预示了银(I)二聚体在可见光吸收和激发态反应中的应用。
Well-defined dinuclear silver(I) complexes have been targeted for applications in catalysis and materials chemistry, and the effect of close silver–silver interactions on electronic structure remains an area of active inquiry. In this study, we describe the synthesis, structure, and photophysical properties of dimeric silver complexes featuring a redox-active naphthyridine diimine ligand. Unusually for silver(I), these complexes display absorption features in the visible region due to metal–metal to ligand charge transfer (MMLCT) transitions, which arise from the combination of close silver–silver interactions and low-lying ligand π* orbitals. The complexes’ photophysical properties are explored via a combination of spectroscopic and computational studies, revealing MMLCT excited state lifetimes that exceed 1 μs. These results portend previously unforeseen applications of silver(I) dimers in visible light absorption and excited state reactivity.