Gholipour-Ranjbar Habib, Jena Puru, Laskin Julia
Department of Chemistry, Purdue University, West Lafayette, IN, 47906, USA.
Department of Physics, Virginia Commonwealth University, Richmond, VA, 23284, USA.
Commun Chem. 2022 Oct 19;5(1):130. doi: 10.1038/s42004-022-00750-z.
Functionalization of metal-chalcogenide clusters by either replacing core atoms or by tuning the ligand is a powerful technique to tailor their properties. Central to this approach is understanding the competition between the strength of the metal-ligand and metal-metal interactions. Here, using collision-induced dissociation of atomically precise metal sulfide nanoclusters, CoMSL (L = PEt, M = Mn, Fe, Co, Ni) and CoFeSL (x = 1-3), we study the effect of a heteroatom incorporation on the core-ligand interactions and relative stability towards fragmentation. Sequential ligand loss is the dominant dissociation pathway that competes with ligand sulfide (LS) loss. Because the ligands are attached to metal atoms, LS loss is an unusual dissociation pathway, indicating significant rearrangement of the core prior to fragmentation. Both experiments and theoretical calculations indicate the reduced stability of CoMnSL and CoFeSL towards the first ligand loss in comparison with their CoSL and CoNiSL counterparts and provide insights into the core-ligand interaction.
通过替换核心原子或调整配体来实现金属硫族化物簇的功能化，是一种调整其性质的强大技术。这种方法的核心是理解金属-配体相互作用强度与金属-金属相互作用之间的竞争关系。在这里，我们使用原子精确的金属硫化物纳米簇（CoMSL，L = PEt，M = Mn、Fe、Co、Ni）和CoFeSL（x = 1 - 3）的碰撞诱导解离，研究杂原子掺入对核心-配体相互作用以及碎片化相对稳定性的影响。连续的配体损失是与配体硫化物（LS）损失竞争的主要解离途径。由于配体附着在金属原子上，LS损失是一种不寻常的解离途径，这表明在碎片化之前核心发生了显著的重排。实验和理论计算均表明，与CoSL和CoNiSL对应物相比，CoMnSL和CoFeSL对第一个配体损失的稳定性降低，并为核心-配体相互作用提供了见解。
