Chloride assisted supramolecular assembly of a luminescent gigantic cluster: [Ag 216 S 56 Cl 7 (C[triple bond, length as m-dash]CPh) 98 (H 2 O) 12 ] - with pseudo-T h skeleton and five-shell arrangement

Using a chloride-assisted supramolecular building-block approach, we have employed the molecular Cl@Ag (C[triple bond, length as m-dash]CPh) entity in the construction of a gigantic cluster namely [Ag S Cl (C[triple bond, length as m-dash]CPh) (H O) ][Ag (imidazole)(H O) ](SbF ) (1), which contains the largest discrete organometallic cluster investigated by X-ray crystallography. Based on an icosahedral Cl@Ag kernel, this spheroidal cluster features an unprecedented five-shell structure Cl@Ag @S @Ag @S Cl @Ag with idealized T symmetry. The MALDI-MS, 1D, 2D H NMR, electronic absorption, emission spectra and HR-TEM of 1 were measured. Compound 1 shows intense red luminescence in solution at room temperature (QY = 4.7% in CH Cl ), in addition to its 3.4 nm diameter, which makes it a unique example that fills the gap between small luminescent silver clusters and large luminescent silver nanoparticles.