Dille Sara A, Colston Kyle J, Mogesa Benjamin, Cassell Joseph, Perera Eranda, Zeller Matthias, Basu Partha
School Science, Department of Chemistry and Chemical Biology, Indiana University-Purdue University Indianapolis, 402 N. Blackford St., Indianapolis, IN 462020, USA.
School of Natural Science, Department of Chemistry and Biochemistry, Duquesne University, 600 Forbes Ave., Pittsburgh, PA 15282 USA.
Eur J Inorg Chem. 2021 Mar 12;2021(10):914-922. doi: 10.1002/ejic.202001155. Epub 2021 Jan 18.
We report a series of mononuclear monooxo Mo(IV) complexes possessing either one or two fully oxidized dithiolene ligands; [MoOCl(RDt)][X], ( and ), and MoO(-SCHY)(RDt), ( and ), (R=Me, Pr; X= PF, SbF, BF; Y= H, Cl, F, CF, Me, Bu, OMe). Either four or two quasi-reversible ligand-based redox couples are detected depending upon the number of fully oxidized dithiolene ligands present. The molecular structure of and exhibit a large (47° to 70°) fold angle along the S•••S vector of the dithione ligand. The UV-Vis spectra of and exhibit a low energy charge transfer band at ~540 nm that are red-shifted ~200 nm compared to the spectra of and . Density Functional Theory (DFT) calculations show that the low energy charge transfer band of and is heavily influenced by ligand fold angle. Reducing the fold angle decreases the charge transfer energy, and the transition becomes more ligand-based.
我们报道了一系列具有一个或两个完全氧化的二硫纶配体的单核单氧钼（IV）配合物；[MoOCl(RDt)][X]，（以及），和MoO(-SCHY)(RDt)，（以及），（R = 甲基，丙基；X = PF，SbF，BF；Y = H，Cl，F，CF，甲基，丁基，甲氧基）。根据存在的完全氧化的二硫纶配体的数量，检测到四个或两个基于配体的准可逆氧化还原对。和的分子结构沿着二硫酮配体的S•••S向量呈现出较大的（47°至70°）折叠角。和的紫外可见光谱在约540 nm处呈现出低能量电荷转移带，与和的光谱相比，该带红移了约200 nm。密度泛函理论（DFT）计算表明，和的低能量电荷转移带受配体折叠角的影响很大。减小折叠角会降低电荷转移能量，并且跃迁变得更加基于配体。
