Structurally Flexible Au-Cu Alloy Nanoclusters Enabling Efficient Triplet Sensitization and Photon Upconversion.

Ligand-protected noble-metal nanoclusters exhibit an innately triplet nature and have been recently recognized as emerging platforms for triplet sensitizers of photon upconversion (UC) via triplet-triplet annihilation. Herein, we report that a structurally flexible Au-Cu alloy nanocluster, [AuCu(S-Adm)(DPPM)] (; S-Adm = 1-adamantanethiolate, DPPM = bis(diphenylphosphino)methane), exhibited favorable sensitizer properties and superior UC performance. Contrary to the structurally rigid AuCu(S-Adm)(TPP) (, TPP = triphenylphosphine), exhibited significantly better sensitizer characteristics, such as a near-unity quantum yield for intersystem crossing (ISC), long triplet lifetime (ca. 8 μs), and efficient triplet energy transfer (TET). The efficient ISC of was attributed to the practically negligible activation barriers during the ISC process, which was caused by the spin-orbit interaction between the two isoenergetic isomers predicted by theoretical calculations. A series of aromatic molecules with different triplet energies were used as acceptors to reveal the driving force dependence of the TET rate constant (). This dependency was analyzed to evaluate the triplet energy and sensitization ability of the alloy nanoclusters. The results showed that the maximum value of for was seven times larger than that for , which presumably reflects the structural/electronic fluctuations of during the triplet state residence. The combination of the sensitizer and the 9,10-diphenylanthracene (DPA) annihilator/emitter achieved UC with internal quantum yields of 14% (out of 50% maximum) and extremely low threshold intensities (2-26 mWcm). This performance far exceeds that of and is also outstanding among the organic-inorganic hybrid nanomaterials reported so far.