Obey Tom J N, Singh Mukesh K, Canaj Angelos B, Nichol Gary S, Brechin Euan K, Love Jason B
EaStCHEM School of Chemistry, University of Edinburgh, EH9 3FJ, Edinburgh, United Kingdom.
J Am Chem Soc. 2024 Oct 23;146(42):28658-28662. doi: 10.1021/jacs.4c12188. Epub 2024 Oct 14.
The analysis of intervalence charge transfer (IVCT) in mixed-valence compounds can help understand electron transfer processes that are important in diverse applications such as molecular electronics and artificial photosynthesis. While mixed-valence complexes of the lanthanides are more difficult to access than their transition metal analogues, they have shown IVCT phenomena derived from Robin-Day Class II localized valency or even electronic transitions due to - metal-metal bonding. In contrast, we report here the synthesis, characterization, and computational analysis of a rare, Robin-Day Class III, singly reduced dinuclear Yb complex, which is best viewed as having delocalized oxidation states. In this case, no metal-metal bonding occurs and, for the first time, IVCT in a Robin-Day Class III complex resulting from - transitions is observed.
混合价化合物中的价间电荷转移（IVCT）分析有助于理解电子转移过程，这些过程在分子电子学和人工光合作用等各种应用中至关重要。虽然镧系元素的混合价配合物比其过渡金属类似物更难获得，但它们已表现出源自罗宾-戴II类局域价态的IVCT现象，甚至由于金属-金属键合而产生电子跃迁。相比之下，我们在此报告一种罕见的罗宾-戴III类单还原双核镱配合物的合成、表征和计算分析，该配合物最好被视为具有离域氧化态。在这种情况下，不发生金属-金属键合，并且首次观察到由跃迁导致的罗宾-戴III类配合物中的IVCT。
