Cupriphication of gold to sensitize d ¹⁰ –d ¹⁰ metal–metal bonds and near-unity phosphorescence quantum yields

Abstract

Outer-shell s⁰/p⁰ orbital mixing with d¹⁰ 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 Au₄Cu₂ {[Au₄(μ-C²,N³-EtIm)₄Cu₂(µ-3,5-(CF₃)₂Pz)₂], (4a)}, Au₂Cu {[Au₂(μ-C²,N³-BzIm)₂Cu(µ-3,5-(CF₃)₂Pz)], (1) and [Au₂(μ-C²,N³-MeIm)₂Cu(µ-3,5-(CF₃)₂Pz)], (3a)}, AuCu₂ {[Au(μ-C²,N³-MeIm)Cu₂(µ-3,5-(CF₃)₂Pz)₂], (3b) and [Au(μ-C²,N³-EtIm)Cu₂(µ-3,5-(CF₃)₂Pz)₂], (4b)} and stacked Au₃/Cu₃ {[Au(μ-C²,N³-BzIm)]₃[Cu(µ-3,5-(CF₃)₂Pz)]₃, (2)} form upon reacting Au₃ {[Au(μ-C²,N³-(N-R)Im)]₃ ((N-R)Im = imidazolate; R = benzyl/methyl/ethyl = BzIm/MeIm/EtIm)} with Cu₃ {[Cu(μ-3,5-(CF₃)₂Pz)]₃ (3,5-(CF₃)₂Pz = 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 d¹⁰-d¹⁰ polar-covalent bond with ligand-unassisted Cu(I)-Au(I) distances of 2.8750(8) Å each-the shortest such an intermolecular distance ever reported between any two d¹⁰ centers so as to deem it a "metal-metal bond" vis-à-vis "metallophilic interaction." Density-functional calculations estimate 35-43 kcal/mol binding energy, akin to typical M-M single-bond energies. Congruently, FTIR spectra of 4a show multiple far-IR bands within 65-200 cm^-1, assignable to <i>v</i>_Cu-Au as validated by both the Harvey-Gray method of crystallographic-distance-to-force-constant correlation and dispersive density functional theory computations. Notably, the heterobimetallic complexes herein exhibit photophysical properties that are favorable to those for their homometallic congeners, due to threefold-to-twofold symmetry reduction, resulting in cuprophilic sensitization in extinction coefficient and solid-state photoluminescence quantum yields approaching unity (Φ_PL = 0.90-0.97 vs. 0-0.83 for Au₃ and Cu₃ precursors), which bodes well for potential future utilization in inorganic and/or organic LED applications.