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![[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Bulky Aryl Isocyanides and Secondary-Sphere Ag(I) Improve Blue Phosphorescence in Pt(II) Acetylide Complexes
1Department of Chemistry, University of Houston, Houston, Texas 77204-5003, United States.
None:
In this work, we describe blue-phosphorescent platinum acetylide complexes of the formula cis-[Pt(CN-Ar)2(C≡C-2-py)2] (3-5), where C≡C-2-py is 2-pyridylacetylide and CN-Ar is an aryl isocyanide with progressively increasing steric bulk. Treatment of these complexes with silver(I) tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (AgBArF4) results in chelation of the Ag(I) ion by the two 2-pyridylacetylide ligands. Photophysical studies in solution and PMMA films, recorded at different concentrations, generalize the previous observation that coordination of Ag(I) improves the radiative rate constant and photoluminescence quantum yield (ΦPL), by more than 2-fold in each case, and demonstrate two key effects of the bulky aryl isocyanides. First, in the silver-free precursor complexes, the aryl isocyanide ligands bring about an enhancement in ΦPL when compared to alkyl isocyanide ligands. Furthermore, in the silver-bound complexes, steric bulk on the aryl isocyanides is an important factor for inhibiting aggregation in film samples, preserving deep-blue phosphorescence and promoting a further increase in ΦPL, maximizing at ΦPL = 0.22 with the most sterically crowded isocyanide.
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