Halides-Promoted Construction and Assembly of Copper Nanoclusters Capped by Bulky Zwitterionic Ligands

Abstract Surface-passivating agents are pivotal in determining the structures and associated properties of monolayer-protected metal nanoclusters (NCs). Herein, by utilizing bulky zwitterionic sulfur-containing ligands, namely (C6H5)3PCH2CH2CH2SNaBr (NaL∙Br) and along with halides-induced tactics, we isolated two novel copper NCs Cu14L6Br12Cl2 (1), Cu15L6BrI14 (2) as well as an assembly compound [Cu16.5L6Br16.5]n (3). X-ray diffraction analysis reveals that compound 3 is formed through the assembly of two infinite 1D chains, composed of monomers Cu14L6Br14 and Cu16L6Br16 respectively. Compounds 1, 2 and the monomers of 3 possess similar Cu12S6X6 arrangement (X = Cl, Br and I), and all three compounds demonstrate reversible luminescence thermochromic behaviors. The study enriches the structure of zwitterionic ligand-protected copper NCs, and elucidates the regulatory role of halides in modulating structures.