Synthesis, Structure, and Characterization of Dinuclear Copper(I) Halide Complexes with PAN Ligands Featuring Exciting Photoluminescence Properties

A series of highly luminescent dinuclear copper(I) complexes has been synthesized in good yields using a modular ligand system of easily accessible diphenylphosphinopyridine-type PAN ligands. Characterization of these complexes via X-ray crystallographic studies and elemental analysis revealed a dinuclear complex structure with a butterfly-shaped metal-halide core. The complexes feature emission covering the visible spectrum from blue to red together with high quantum yields up to 96%. Density functional theory calculations show that the HOMO consists mainly of orbitals of both the metal core and the bridging halides, while the LUMO resides dominantly on the heterocyclic part of the P boolean AND N ligands. Therefore, modification of the heterocyclic moiety of the bridging ligand allows for systematic tuning of the luminescence wavelength. By increasing the aromatic system of the N-heterocycle or through functionalization of the pyridyl moiety, complexes with emission maxima from 481 to 713 nm are obtained. For a representative compound, it is shown that the ambient-temperature emission can be assigned as a thermally activated delayed fluorescence, featuring an attractively short emission decay time of only 6.5 mu s at phi(PL) = 0.8. It is proposed to apply these compounds for singlet harvesting in OLEDs.