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The structural, photophysical and electrochemical properties of three luminescent 2-coordinate coinage metal (i.e., M = Cu, Ag, Au) complexes bearing a sterically bulky benzimidazolyl carbene, 1,3-bis(2,6-diisopropylphenyl)-1-H-benzo[d]imidazol-2-ylidene ( BZI ), and carbazolide (Cz) as the anionic ligand were investigated. All the complexes emit in the deep blue region (~430 nm) with relatively narrow spectra (full width at half maximum = 44 nm, 2,300 cm −1 ) characterized by vibronic fine structure in nonpolar media (methylcyclohexane at room temperature), and with high photoluminescence quantum yields (Φ PL  > 80%) and radiative rate constants ( k   r   ~ 7.8 × 10 5  s −1 ). The luminescence is solvatochromic, undergoing a red-shift in a polar solvent (CH 2 Cl 2 ) at room temperature that are accompanied by a decrease in quantum yields (Φ PL  < 23%) and radiative rate constants ( k   r   < 4.0 × 10 4  s −1 ), whereas the non-radiative rate constants remain nearly constant ( k   nr   ~ 1.0 × 10 5  s −1 ). The radiative rate is controlled via thermally assisted delayed fluorescence (TADF) and temperature-dependent luminescence studies of the gold complex ( Au  BZI ) in methylcyclohexane solution reveal an energy difference between the lowest singlet and triplet excited states of 920 cm −1 . An organic light-emitting diode (OLED) fabricated using  Au  BZI  as a luminescent dopant has an external quantum efficiency of 12% and narrow, deep-blue emission (CIE = 0.16, 0.06).

Highly Efficient Deep Blue Luminescence of 2-Coordinate Coinage Metal Complexes Bearing Bulky NHC Benzimidazolyl Carbene