Photoactive Metal-to-Ligand Charge Transfer Excited States in 3d6 Complexes with Cr0, MnI, FeII, and CoIII,Journal of the American Chemical Society

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Photoactive Metal-to-Ligand Charge Transfer Excited States in 3d6 Complexes with Cr0, MnI, FeII, and CoIII
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-02-21 , DOI: 10.1021/jacs.2c13432
Narayan Sinha ₁ , Oliver S Wenger ₁

Affiliation

Many coordination complexes and organometallic compounds with the 4d⁶ and 5d⁶ valence electron configurations have outstanding photophysical and photochemical properties, which stem from metal-to-ligand charge transfer (MLCT) excited states. This substance class makes extensive use of the most precious and least abundant metal elements, and consequently there has been a long-standing interest in first-row transition metal compounds with photoactive MLCT states. Semiprecious copper(I) with its completely filled 3d subshell is a relatively straightforward and well explored case, but in 3d⁶ complexes the partially filled d-orbitals lead to energetically low-lying metal-centered (MC) states that can cause undesirably fast MLCT excited state deactivation. Herein, we discuss recent advances made with isoelectronic Cr⁰, Mn^I, Fe^II, and Co^III compounds, for which long-lived MLCT states have become accessible over the past five years. Furthermore, we discuss possible future developments in the search for new first-row transition metal complexes with partially filled 3d subshells and photoactive MLCT states for next-generation applications in photophysics and photochemistry.

中文翻译：

具有 Cr0、MnI、FeII 和 CoIII 的 3d6 配合物中的光活性金属到配体电荷转移激发态

^{许多具有 4d 6}和 5d ⁶价电子构型的配位化合物和有机金属化合物具有出色的光物理和光化学性质，这些性质源于金属到配体电荷转移 (MLCT) 激发态。该物质类别广泛使用最珍贵和最不丰富的金属元素，因此长期以来人们一直对具有光活性 MLCT 状态的第一行过渡金属化合物感兴趣。具有完全填充的 3d 子壳的半贵铜 (I) 是一个相对简单且经过充分探索的案例，但在 3d ⁶络合物部分填充的 d 轨道导致能量低的金属中心 (MC) 状态，这可能导致不希望的快速 MLCT 激发态失活。在此，我们讨论了等电子 Cr ⁰、Mn ^I、Fe ^II和 Co ^III化合物的最新进展，在过去五年中，这些化合物的长寿命 MLCT 状态已成为可能。此外，我们讨论了在寻找具有部分填充的 3d 子壳和光活性 MLCT 状态的新的第一行过渡金属配合物方面可能的未来发展，以用于光物理学和光化学的下一代应用。

更新日期：2023-02-21

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