Gholipour-Ranjbar Habib, Fang Hong, Guan Jintong, Peters D'Angelo, Seifert Audra, Jena Puru, Laskin Julia
Department of Chemistry, Purdue University, West Lafayette, IN, 47906, USA.
Department of Physics, Virginia Commonwealth University, Richmond, VA, 23284, USA.
Small. 2021 Jul;17(27):e2002927. doi: 10.1002/smll.202002927. Epub 2020 Nov 8.
Atom-by-atom substitution is a promising strategy for designing new cluster-based materials, which has been used to generate new gold- and silver-containing clusters. Here, the first study focused on atom-by-atom substitution of Fe and Ni to the core of a well-defined cobalt sulfide superatom [Co S L ] ligated with triethylphosphine (L = PEt ) to produce [Co MS L ] (M = Fe, Ni) is reported. Electrospray ionization mass spectrometry confirms the substitution of 1-6 Fe atoms with the single Fe-substituted cluster being the dominant species. The Fe-substituted clusters oxidize in solution to generate dicationic species. In contrast, only a single Ni-substituted cluster is observed, which remains stable as a singly charged species. Collision-induced dissociation experiments indicate the reduced stability of the [Co FeS L ] toward ligand loss in comparison with the unsubstituted and Ni-substituted counterparts. Density functional theory calculations provide insights into the effect of metal atom substitution on the stability and electronic structures of the clusters. The results indicate that Fe and Ni have a different impact on the electronic structure, optical, and magnetic properties, as well as ligand-core interaction of [Co S L ]. This study extends the atom-by-atom substitution strategy to the metal chalcogenide superatoms providing a direct path toward designing novel atomically precise core-tailored superatoms.
逐个原子取代是设计新型簇基材料的一种有前景的策略，该策略已被用于生成新的含金和银的簇。在此，报道了第一项聚焦于将铁和镍逐个原子取代到与三乙膦（L = PEt₃）配位的明确的硫化钴超原子[Co₉S₈L₄]核心上以生成[Co₉MₓS₈L₄]（M = Fe，Ni）的研究。电喷雾电离质谱证实了1 - 6个铁原子的取代，其中单铁取代的簇是主要物种。铁取代的簇在溶液中氧化生成二价阳离子物种。相比之下，仅观察到单个镍取代的簇，其作为单电荷物种保持稳定。碰撞诱导解离实验表明，与未取代和镍取代的对应物相比，[Co₉FeₓS₈L₄]对配体损失的稳定性降低。密度泛函理论计算深入了解了金属原子取代对簇的稳定性和电子结构的影响。结果表明，铁和镍对[Co₉S₈L₄]的电子结构、光学和磁性以及配体 - 核心相互作用有不同的影响。这项研究将逐个原子取代策略扩展到金属硫族化物超原子，为设计新型原子精确的核心定制超原子提供了一条直接途径。
