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Published on: September 12, 2014
Photon Upconversion Enhanced by Ag29 Nanocluster Sensitizers and Multifunctional P(DPA)3 Acting as Triplet Mediator,
Masaaki Mitsui1, Yudai Miura1, Ryuichi Oyaizu2
1Department of Chemistry, College of Science, Rikkyo University, 3-34-1, Nishiikebukuro, Toshima-ku, Tokyo 171-8501, Japan.
Abstract:
The [Ag29(BDT)12]3- nanocluster (Ag29, BDT = 1,3-benzenedithiolate) is renowned for its high stability, photoluminescence, and ability to accommodate up to four phosphine compounds as secondary ligands. Herein, the multichromophoric phosphine derivative P(DPA)3, bearing three 9,10-diphenylanthracene (DPA) units, was employed to serve triple roles: triplet-energy mediator ligand, annihilator, and emitter. By adding an excess amount of P(DPA)3 to Ag29, a solution was prepared containing [Ag29(BDT)12[P(DPA)3]n]3- (Ag29PDPA, n = 1-4) complexes coexisting with unbound (free) P(DPA)3 molecules. This enabled efficient intra- and intermolecular triplet energy transfer from photoexcited Ag29, first to the bound and then to the unbound P(DPA)3. Under 532 nm excitation, the system achieved a green-to-blue UC internal quantum yield of 24.0% (48% normalized to the 100% maximum) and a significantly low threshold intensity of 2.0 mW cm-2. Remarkably, this performance rivals that of the benchmark Pt(II)-octaethylporphine/DPA pair, establishing the Ag29PDPA/P(DPA)3 combination as a high-performing green-to-blue UC system.
