Luminescent molecular copper(I) alkynyl open cubes: synthesis, structural characterization, electronic structure, photophysics, and photochemistry.

A novel class of tetranuclear copper(I) alkynyl complexes with an "open-cube" structure was synthesized. The crystal structure of [Cu4{P(p-MeC6H4)3}4(mu3-eta(1),eta(1),eta(2)-C[triple bond]C-p-MeOC6H4)3]PF6 was determined. These complexes were found to display dual emission behavior.

Synthesis, structure and luminescence studies of heterometallic gold(I)-copper(I) and -silver(I) alkynyl clusters/aggregates.

A series of pentanuclear gold(I)-copper(I) and -silver(I) mixed-metal alkynyl complexes, [(n)Bu(4)N][Au(3)M(2)(C triple bond CC(6)H(4)R-p)(6)] [M = Cu, R = OMe, O(n)Bu, O(n)Hex, Me, Et; M = Ag, R = Et, O(n)Hex] have been synthesized. The complexes were found to be emissive both in the solid state and in fluid solutions. DFT calculations at the B3LYP level of theory were performed on [Au(3)M(2)(C triple bond CC(6)H(4)Me-p)(6)](-) (M = Cu, Ag) to provide an understanding on the electronic structure of the complexes.

Molecular design of luminescence ion probes for various cations based on weak gold(I)...gold(I) interactions in dinuclear gold(I) complexes.

A series of luminescent dinuclear gold(I) complexes with different crown ether pendants, [Au(2)(PwedgeP)(S-B15C5)(2)] [S-B15C5 = 4'-mercaptobenzo-15-crown-5, P(wedge)P = bis(dicyclohexylphosphino)methane (dcpm) (1), bis(diphenylphosphino)methane (dppm) (2)] and [Au(2)(P(wedge)P)(S-B18C6)(2)] [S-B18C6 = 4'-mercaptobenzo-18-crown-6, P(wedge)P = dcpm (3), dppm (4)], and their related crown-free complexes, [Au(2)(P(wedge)P)(SC(6)H(3)(OMe)(2)-3,4)(2)] [P(wedge)P = dcpm (5), dppm (6)], were synthesized. The low-energy emission of the mercaptocrown ether-containing gold(I) complexes are tentatively assigned as originated from states derived from a S --> Au ligand-to-metal charge transfer (LMCT) transition. The crown ether-containing gold(I) complexes showed specific binding abilities toward various metal cations according to the ring size of the crown pendants.

Proof of Potassium Ions by Luminescence Signaling Based on Weak Gold-Gold Interactions in Dinuclear Gold(I) Complexes.

Two versatile luminescence ion probes for potassium ions have been designed based on the "switching on and off" of the gold-gold interaction. Addition of potassium ions to the gold(I) complexes [Au (R PCH PR )(S-benzo[15]crown-5) ] (see the picture; R=Ph, cyclohexyl; M =K ) give rise to an intense red luminescence.