Effect of Gold(I) on the Room-Temperature Phosphorescence of Ethynylphenanthrene

The synthesis of two series of gold(I) complexes with the general formulae PR₃ -Au-C≡C-phenanthrene (PR₃ =PPh₃ (1 a/2 a), PMe₃ (1 b/2 b), PNaph₃ (1 c/2 c)) or (diphos)(Au-C≡C-phenanthrene)₂ (diphos=1,1-bis(diphenylphosphino)methane, dppm (1 d/2 d), 1,4-bis(diphenylphosphino)butane, dppb (1 e/2 e)) has been realized. The two series differ in the position of the alkynyl substituent on the phenanthrene chromophore, being at the 9-position (9-ethynylphenanthrene) for the L1 series and at the 2-position (2-ethynylphenanthrene) for the L2 series. The compounds have been fully characterized by ¹ H, ³¹ P NMR, and IR spectroscopy, mass spectrometry, and single-crystal X-ray diffraction resolution in the case of compounds 1 a, 1 e, 2 a, and 2 c. The emissive properties of the uncoordinated ligands and corresponding complexes have been studied in solution and within organic matrixes of different polarity (polymethylmethacrylate and Zeonex). Room-temperature phosphorescence (RTP) is observed for all gold(I) complexes whereas only fluorescence can be detected for the pure organic chromophore. In particular, the L2 series presents better luminescent properties regarding the intensity of emission, quantum yields, and RTP effect. Additionally, although the inclusion of all the compounds in organic matrixes induces an enhancement of the observed RTP owing to the decrease in non-radiative deactivation, only the L2 series completely suppresses the fluorescence, giving rise to pure phosphorescent materials.