We report the synthesis of novel perhalophenyl three-coordinated gold(I) complexes using 1,2-bis-(diphenylphosphino)benzene (dppBz) as the chelating ligand and [AuR(tht)] (R = C 6 F 5 , C 6 Cl 2 F 3 , C 6 Cl 5 ) as the perhalophenyl− gold(I) source, leading to [AuR(dppBz)] (R = C 6 F 5 (1), C 6 Cl 2 F 3 (2), C 6 Cl 5 (3)) complexes. The solid-state structures of compounds 2 and 3 consist of discrete three-coordinated Au(I) complexes, which show a distorted trigonal planar geometry for the gold center with dissimilar Au−P distances. The distorted structural arrangement is closely related to its photophysical properties. The studied complexes display very intense emissions at room temperature (RT) and at 77 K in the solid state. Studies of the emissive properties of the complexes at different temperatures suggest that the emissions are phosphorescent at 77 K and exhibit thermally activated delayed fluorescence (TADF) at RT. Firstprinciple calculations of the photophysical processes yielded rate constants for intersystem crossing and reverse intersystem crossing that are in excellent agreement with experimental data.

New perhalophenyl three-coordinated gold(I) complexes using the chelate ligand 1,2-bis(diphenylphosphino)benzene (dppBz) and [AuR(tht)] (R = C6F5 (1), o-C6BrF4 (2), p-C6BrF4 (3), o-C6F4I (4), p-C6F4I (5); tht = tetrahydrothiophene) have been...

New luminescent heterometallopolymers [(Au‐C6F5)m(AgOSO2CF3)n (PVP)] with different Au:Ag molar ratios were synthesized. The luminescent emissions of these polymers are strongly dependent on the temperature, excitation wavelengths, and the Au(I):Ag(I) molar ratio. The incorporation of a precise amount of Ag(I) atoms in the backbone of [(Au‐C6F5)m(PVP)] metallopolymer allows a controlled tuning of the emission energy in the green‐blue range.

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