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 [Co6S8L6]+ ligated with triethylphosphine (L = PEt3) to produce [Co5MS8L6]+ (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 [Co5FeS8L6]+ 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 [Co6S8L6]. 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.

Although semiconducting ferromagnetism has been experimentally discovered in two-dimensional (2D) crystals, the spin coupling is still quite weak, which leads to a rather low Curie temperature (T C ). Thus, it is quite confused whether the ferromagnetism in semiconductors can survive under room temperature. Here, through isovalent alloying, we propose that the semiconducting ferromagnetism of 2D MnS 2 can be significantly enhanced with T C improved higher than room temperature. Based on first-principles calculations, we systematically studied the properties of original MnS 2 and the isovalent alloying systems Mn x Re 1−x S 2 . The spin coupling is significantly enhanced by introducing Mn−Re virtual bonds, and the highest T C of the system reaches 360 K. Besides this, a tensile strain will further enhance the ferromagnetic couplings as well as the uniaxial magnetic anisotropy, which is important for the stabilization of longrange ferromagnetic order in a 2D system. Our results not only broaden the family of 2D ferromagnetic semiconductors but also provide the direct clues to prepare such hightemperature magnetic materials for promising applications in spintronics.

Transition dipole moment is suggested as a bridge between band structure and optical absorption in semiconductor photocatalysts and as referential descriptor for interlayer photoexcitation in layered heterostructures.

Finding photocatalysts that fully utilize the visible solar light to split water into hydrogen and oxygen has been a challenging problem for a long time.