Cupriphication of gold to sensitize d-d metal-metal bonds and near-unity phosphorescence quantum yields.

Outer-shell s/p orbital mixing with d orbitals and symmetry reduction upon cupriphication of cyclic trinuclear trigonal-planar gold(I) complexes are found to sensitize ground-state Cu(I)-Au(I) covalent bonds and near-unity phosphorescence quantum yields. Heterobimetallic AuCu {[Au(μ-C,N-EtIm)Cu(µ-3,5-(CF)Pz)], (4a)}, AuCu {[Au(μ-C,N-BzIm)Cu(µ-3,5-(CF)Pz)], (1) and [Au(μ-C,N-MeIm)Cu(µ-3,5-(CF)Pz)], (3a)}, AuCu {[Au(μ-C,N-MeIm)Cu(µ-3,5-(CF)Pz)], (3b) and [Au(μ-C,N-EtIm)Cu(µ-3,5-(CF)Pz)], (4b)} and stacked Au/Cu {[Au(μ-C,N-BzIm)][Cu(µ-3,5-(CF)Pz)], (2)} form upon reacting Au {[Au(μ-C,N-(N-R)Im)] ((N-R)Im = imidazolate; R = benzyl/methyl/ethyl = BzIm/MeIm/EtIm)} with Cu {[Cu(μ-3,5-(CF)Pz)] (3,5-(CF)Pz = 3,5-bis(trifluoromethyl)pyrazolate)}. The crystal structures of 1 and 3a reveal stair-step infinite chains whereby adjacent dimer-of-trimer units are noncovalently packed via two Au(I)⋯Cu(I) metallophilic interactions, whereas 4a exhibits a hexanuclear cluster structure wherein two monomer-of-trimer units are linked by a genuine d-d polar-covalent bond with ligand-unassisted Cu(I)-Au(I) distances of 2.

Adsorption and molecular siting of CO, water, and other gases in the superhydrophobic, flexible pores of FMOF-1 from experiment and simulation.

FMOF-1 is a flexible, superhydrophobic metal-organic framework with a network of channels and side pockets decorated with -CF groups. CO adsorption isotherms measured between 278 and 313 K and up to 55 bar reveal a maximum uptake of 6.16 mol kg (11.

Rigidifying fluorescent linkers by metal-organic framework formation for fluorescence blue shift and quantum yield enhancement.

We demonstrate that rigidifying the structure of fluorescent linkers by structurally constraining them in metal-organic frameworks (MOFs) to control their conformation effectively tunes the fluorescence energy and enhances the quantum yield. Thus, a new tetraphenylethylene-based zirconium MOF exhibits a deep-blue fluorescent emission at 470 nm with a unity quantum yield (99.9 ± 0.