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The photophysical properties of four, two-coordinate, linear diamidocarbene copper(i) complexes, [(DAC)2Cu][BF4] (1), (DAC)CuOSiPh3 (2), (DAC)CuC6F5 (3) and (DAC)Cu(2,4,6-Me3C6H2) (4) (DAC = 1,3-bis(2,4,6-trimethylphenyl)-5,5-dimethyl-4,6-diketopyrimidinyl-2-ylidene) have been investigated. Complex 1 shows a high photoluminescence quantum efficiency (ΦPL) in both the solid state (ΦPL = 0.85) and in CH2Cl2 solution (ΦPL = 0.65). The emission band of 1, both as a crystalline solid and in solution, is narrow (fwhm = 2300 cm−1) relative to the emission bands of 2 (fwhm = 2900 cm−1) and 3 (fwhm = 3700 cm−1). Complexes 2 and 3 are each brightly luminescent in the solid state (ΦPL = 0.62 and 0.18, respectively), but markedly less so in CH2Cl2 solution (ΦPL = 0.03 and ＜0.01, respectively). Complex 4 is not emissive in either the solid state or in solution. Phosphorescence of 1 in CH2Cl2 solution shows negligible quenching by oxygen in CH2Cl2 solution. This insensitivity to quenching is attributed to the excited state redox potential being insufficient for electron transfer to oxygen. [ABSTRACT FROM AUTHOR]