Luminescent CdSe Superstructures: A Nanocluster Superlattice and a Nanoporous Crystal.

Superstructures, combining nanoscopic constituents into micrometer-size assemblies, have a great potential for utilization of the size-dependent quantum-confinement properties in multifunctional electronic and optoelectronic devices. Two diverse superstructures of nanoscopic CdSe were prepared using solvothermal conversion of the same cadmium selenophenolate precursor (MeN)[Cd(SePh)]: the first is a superlattice of monodisperse [CdSe(SePh)(dmf)] nanoclusters; the second is a unique porous CdSe crystal. Nanoclusters were crystallized as cubic crystals (≤0.

A Controlled Route to a Luminescent 3 d -5 d Sulfido Cluster Containing Unique AuCu (μ -S) Motifs.

The first examples of gold(I) trimethylsilylchalcogenolate complexes were synthesized and their reactivity showcased in the preparation of a novel gold-copper-sulfur cluster [Au Cu S (dppm) ] (dppm=bis(diphenylphosphino)methane). The unprecedented structural chemistry of this compound gives rise to interesting optoelectronic properties, including long-lived orange luminescence in the solid state. Through time-dependent density functional theory calculations, this emission is shown to originate from ligand-to-metal charge transfer facilitated by Au⋅⋅⋅Cu metallophilic bonding.

Stable -ESiMe3 Complexes of Cu(I) and Ag(I) (E=S, Se) with NHCs: Synthons in Ternary Nanocluster Assembly.

As a part of efforts to prepare new "metallachalcogenolate" precursors and develop their chemistry for the formation of ternary mixed-metal chalcogenide nanoclusters, two sets of thermally stable, N-heterocyclic carbene metal-chalcogenolate complexes of the general formula [(IPr)Ag-ESiMe3] (IPr=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene; E=S, 1; Se, 2) and [(iPr2-bimy)Cu-ESiMe3]2 (iPr2-bimy=1,3-diisopropylbenzimidazolin-2-ylidene; E=S, 4; Se, 5) are reported. These are prepared from the reaction between the corresponding carbene metal acetate, [(IPr)AgOAc] and [(iPr-bimy)CuOAc] respectively, and E(SiMe3 )2 at low temperature. The reaction of [(IPr)Ag-ESiMe3] 1 with mercury(II) acetate affords the heterometallic complex [{(IPr)AgS}2Hg] 3 containing two (IPr)Ag-S(-) fragments bonded to a central Hg(II), representing a mixed mercury-silver sulfide complex.