One pseudopentasupertetrahedral chalcogenidometalate cluster, [(BuSn)3SnCd4S13(OH)]·6­(H+DMP) (PPS-1; H+DMP = protonated 3,5-dimethylpiperidine), has been isolated by use of an organotin precursor. They are arranged to generate two types of tetrahedrally patterned cages, which further interconnect to form a diamond network. Owing to the covalent attachment of abundant alkyl groups, PPS-1 exhibits excellent hydrophobicity and could be used as an assembly substance for building liquid marbles.

Three novel heterometallic oxysulfide clusters with different coordination small organic molecules have been solvothermally synthesized and structurally characterized, i.e., [( n BuSn)3La(DTT)3(DETA)(L)] ( n BuSn = n-butyltin; DTT = 1,4-dithiothreitol; DETA = diethylenetriamine; L = N,N-dimethylformamide (DMF) (1), N-methyl pyrrolidone (NMP) (2), and N-methyl formanilide (MFA) (3)). These clusters are a bowl-shaped structure, composed of a central DETA-coordinated La3+ cation fixed in the triangle ring, [( n BuSn)3(DTT)3], and an amide molecule bonded to La3+ confined inside the bowl. The coordinated amides can be changed and served as a molecular regulator to optimize the microsteric interaction between the clusters and further the physicochemical property. Remarkably, the crystals of 1 exhibit strong blue-violet light emission with the photoluminescence quantum yield (PLQY) of 3.69%, which significantly exceeds than that of 2 and 3 and most of the other organotin oxysulfide clusters. Theoretical calculations and Hirshfeld surface analyses indicate that the weak amide-oriented intercluster interactions of the compounds can regulate their photoluminescence (PL) efficiency. This work provides a paradigm to reveal the relationships between its PL and structurally fine-tuned coordination species.

Two copper(I)-sulfide clusters were synergistically modified by alkylthiols and conjugated N,S-heterocyclic ligands, i.e., Cu 6 ( t BuS) 2 (MBIZ) 4 (designated as Cu 6 ) and Cu 8 ( t BuS) 4 (MBIZ) 4 • CH 3 OH•2H 2 O (designated as Cu 8 ) (MBIZ = 2-mercaptobenzimidazole; t BuS = tert-butyl mercaptan). Introducing more thiol ligands led to further growth of the cluster core, resulting in the transformation from an octahedral to a di-tetrahedral configuration, accompanied by a slight increase in the Cu••• Cu distance. Notably, both clusters demonstrate high chemical stability and superhydrophobicity as a result of the modification with surface ligands, being stable at least 1 week in a wide range of pH (1−14 for Cu 6 and 3−11 for Cu 8 ). Moreover, Cu 8 exhibited near-infrared (NIR) photoluminescence (PL) emission and better third-order nonlinear optical (NLO) performance, with nonlinear absorption coefficients (β) of 3.5 × 10 −10 m/W, 3.5 times than that of Cu 6 and superior to the majority of crystalline chalcogenide semiconductors. Theoretical calculations indicate that the organic ligands and cluster core jointly optimize the electronic configuration in a manner that regulates the optical properties. This work provides a new perspective into understanding the relationship between cluster core/surface compositions and optical properties at an atomically precise level, which is instrumental in the accurate design and synthesis of stable and efficient third-order NLO materials.