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Gold(I) Complexes with Bulky Phosphanes
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Resumo(s)
Two families of mononuclear gold(I) complexes featuring Au-chromophore units, with chromophores being carbazole (a), phenanthrene (b), or dibenzofuran (c), were synthesized. The Au(I) atoms are coordinated to two phosphanes, either PMe2ArXyl2 (ArXyl2 = 2,6-C6H3-(2,6-C6H3-Me2)2) (P1) or the bulkier PCyp2ArXyl2 (Cyp = cyclopentyl) (P2). The photophysical properties of these complexes were extensively studied, with a particular focus on the effects of phosphane bulkiness and chromophore electron-donating capacity on triplet state quantum yields (ΦT). Nanosecond-laser flash photolysis measurements were employed to calculate ΦT. Time-dependent density functional theory (TD-DFT) calculations supported the absorption and emission assignments, providing insights into the electronic state gaps involved in photophysical processes and their relative populations. The parent complex AuClP2 in combination with NaBAr4F, as a chloride scavenger, served as an efficient catalyst for the hydroamination of a variety of alkynes and amines, under mild conditions and with low Au loading (0.1-0.2 mol %). Luminescent studies allowed us to check the active catalytic species.
Descrição
Funding Information: The authors are grateful to the Ministerio de Ciencia e Innovación of Spain (project numbers PID2022-139296NB-I00, PID2020-113797RB-C22, and CNS2022-135816) and the Spanish network, Organometallic Chemistry for Sustainable Solutions − OASIS (RED2022-134074-T). This article is also based upon work from COST Action CA22131, LUCES Supramolecular LUminescent Chemosensors for Environmental Security, supported by COST (European Cooperation in Science and Technology). This research used resources of the ALBA synchrotron. The corresponding crystallographic measurements were performed with the collaboration of ALBA staff at BL13-XALOC beamline. Publisher Copyright: © 2025 American Chemical Society.
Palavras-chave
Physical and Theoretical Chemistry Inorganic Chemistry