A New Synthetic Methodology in the Preparation of Bimetallic Chalcogenide Clusters via Cluster-to-Cluster Transformations

A decanuclear silver chalcogenide cluster, [Ag10(Se){Se2P(OiPr)2}8] (2) was isolated from a hydride-encapsulated silver diisopropyl diselenophosphates, [Ag7(H){Se2P(OiPr)2}6], under thermal condition. The time-dependent NMR spectroscopy showed that 2 was generated at the first three hours and the hydrido silver cluster was completely consumed after thirty-six hours. This method illustrated as cluster-to-cluster transformations can be applied to prepare selenide-centered decanuclear bimetallic clusters, [CuxAg10-x(Se){Se2P(OiPr)2}8] (x = 0–7, 3), via heating [CuxAg7−x(H){Se2P(OiPr)2}6] (x = 1–6) at 60 °C. Compositions of 3 were accurately confirmed by the ESI mass spectrometry. While the crystal 2 revealed two un-identical [Ag10(Se){Se2P(OiPr)2}8] structures in the asymmetric unit, a co-crystal of [Cu3Ag7(Se){Se2P(OiPr)2}8]0.6[Cu4Ag6(Se){Se2P(OiPr)2}8]0.4 ([3a]0.6[3b]0.4) was eventually characterized by single-crystal X-ray diffraction. Even though compositions of 2, [3a]0.6[3b]0.4 and the previous published [Ag10(Se){Se2P(OEt)2}8] (1) are quite similar (10 metals, 1 Se2−, 8 ligands), their metal core arrangements are completely different. These results show that different synthetic methods by using different starting reagents can affect the structure of the resulting products, leading to polymorphism.

Structural Transformation and Luminescence Response of Magic-Size Silver(I) Chalcogenide Clusters via Ligand-Exchange

Structural transformations of nanoclusters provide a platform to tune their properties and understand the fundamental science due to their intimate structure–property correlation. Here, we present a ligand-exchange induced growth of...

Twist Tetrahedral-Tilting Structure Built from Photoluminescent Cadmium Chalcogenide Clusters

The newly synthesized cadmium chalcogenide ternary cluster is composed by six [S3Se]2− tetrahedron units, coordinated with six Cd2+ cations. The potential cavity, calculated by the PLATON program, occupied 38.1% of crystal cell volume. The charge of unit cell is neutral. Therefore, the unit cell formula is determinate as [Cd6S18Se6]. Two strong solid-state luminescence peaks, centered at 450 nm and 498 nm, were observed from the ternary [Cd6S18Se6] clusters by λ = 370 nm radiation. The 450 nm peak is due to the porosity property of cadmium chalcogenide clusters. However, the 498 nm peak has not been reported for the cadmium chalcogenide clusters before. In this study, we demonstrate that the 498 nm peak is attributed to the embedded Se atoms confined in the [S3Se]2− unit of [Cd6S18Se6] cluster. The luminescent output from the ternary [Cd8S18Se6] cluster is stable in room temperature for more than 6 months.

Heavy chalcogenide-transition metal clusters as coordination polymer nodes

Recent developments, challenges, and opportunities in using polynuclear transition metal heavy chalcogenide clusters as nodes for coordination polymers.