Chloride assisted supramolecular assembly of a luminescent gigantic cluster: [AgSCl(C[triple bond, length as m-dash]CPh)(HO)] with pseudo-T 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 [AgSCl(C[triple bond, length as m-dash]CPh)(HO)]Ag(imidazole)(HO) (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@SCl@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 CHCl), 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.