Solvent-Controlled Doublet Emission of an Organometallic Gold(I) Complex with a Polychlorinated Diphenyl(4-pyridyl)methyl Radical Ligand: Dual Fluorescence and Enhanced Emission Efficiency.

A paramagnetic, luminescent organometallic gold(I) complex AuI(C6F5)(PyBTM), where PyBTM is a photostable fluorescent polychlorinated diphenyl(4-pyridyl)methyl radical, was prepared, and its crystal and electronic structures and magnetic and optical properties were investigated. Magnetic studies using electron spin resonance spectroscopy and a superconducting quantum interference device magnetometer indicated the existence of S = 1/2 spin per molecule, with the spin density distributed mainly on the PyBTM ligand. The complex exhibited fluorescence in CHCl3 with emission peak wavelength (λem) of 619 nm and the absolute fluorescence quantum yield (ϕem) of 0.04, confirming that AuI(C6F5)(PyBTM) is the first luminescent organometallic complex with a coordinated luminescent radical. Solvent-dependent unique luminescent characteristics were observed in halogenated solvents (CCl4, CHCl3, CH2Cl2, and ClCH2CH2Cl). ϕem decreased, and λem shifted to longer wavelengths as the polarity (dielectric constant) of the solvent increased. Notably, the complex in CCl4 displayed fluorescence with ϕem = 0.23, which was quite high in radicals, while showed dual fluorescence in CH2Cl2 and ClCH2CH2Cl with lifetimes of around 1 and 7 ns for two emissive components. Density functional theory (DFT) and time-dependent (TD)-DFT calculations indicated that the fluorescence occurred from an interligand charge transfer (CT) excited state in CCl4, in which the C6F5 and PyBTM moieties acted as electron donor and acceptor, respectively, while the fluorescence was centered at the PyBTM ligand in the other three solvents. This method, i.e., the formation of an interligand CT state, to enhance ϕem is distinctly different from the methods reported previously. The present study revealed that a coordination bond is available for forming emissive CT excited states that lead to high ϕem, providing a novel method with greater capability for realizing highly emissive radicals.