Efficient Visible to Near-UV Photochemical Upconversion Sensitized by a Long Lifetime Cu(I) MLCT Complex

The current investigation compares the photochemical upconversion sensitization properties of two long lifetime Cu(I) metal-to-ligand charge transfer (MLCT) chromophores to 3 distinct anthryl-based triplet acceptors. The sensitizers [Cu(dsbtmp)2](PF6) (1, dsbtmp = 2,9-di(sec-butyl)-3,4,7,8-tetramethyl-1,10-phenanthroline) and [Cu(dsbp)2](PF6) (2, dsbp = 2,9-di(sec-butyl-1,10-phenanthroline) were selectively excited in the presence of anthracene, 9,10-diphenylanthracene (DPA), and 9,10-dimethylanthracene (DMA) in degassed dichloromethane solutions. In all instances, triplet energy transfer was observed from selective excitation of the Cu(I) MLCT chromophore to each respective anthryl species. The bimolecular triplet-triplet energy transfer quenching rate constants were extracted from dynamic Stern-Volmer analyses in each case, yielding values below the diffusion limit in dichloromethane. However, the Stern-Volmer quenching constants (KSV's) were sizable enough (up to ∼2300 M(-1) with 1 as a sensitizer) to support efficient photochemical upconversion. As such, visible to near-UV photochemical upconversion was observed in every instance, along with the anticipated quadratic-to-linear incident light power dependence when pumping at 488 nm. The latter verified that it is indeed sensitized triplet-triplet annihilation responsible for the generation of the anthryl-based singlet fluorescence. Photochemical upconversion quantum efficiencies were evaluated using a relative actinometric method as both a function of incident light power density as well as anthryl acceptor/annihilator concentration. When 1 was used as the sensitizer, upconversion quantum yields as large as 9.2% and 17.8% were observed for DMA and DPA, respectively. Finally, the combination of 1 with DMA was shown to be quite robust, showing no obvious signs of decomposition during 12 h of continuous 488 nm photolysis.