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Direct vs Delayed Triplet Energy Transfer from Organic Semiconductors to Quantum Dots and Implications for Luminescent Harvesting of Triplet Excitons
摘要： Hybrid inorganic-organic materials such as quantum dots (QDs) coupled with organic semiconductors have a wide range of optoelectronic applications, taking advantage of the respective materials strengths. A key area of investigation in such systems is the transfer of triplet exciton states to and from QDs, which has potential applications in the luminescent harvesting of triplet excitons generated by singlet fission, in photocatalysis and photochemical upconversion. While the transfer of energy from QDs to the triplet state of organic semiconductors has been intensely studied in recent years, the mechanism and materials parameters controlling the reverse process, triplet transfer to QDs have not been well investigated. Here, through a combination of steady state and time-resolved optical spectroscopy we study the mechanism and energetic dependence of triplet energy transfer from an organic ligand (TIPS-tetracene carboxylic acid) to PbS QDs. Over and energetic range spanning from exothermic (-0.3 eV) to endothermic (+0.1 eV) triplet energy transfer we find that the triplet energy transfer to the QD occurs through a single step process with a clear energy dependence that is consistent with an electron exchange mechanism as described by Marcus-Hush theory. In contrast, the reverse process, energy transfer from the QD to the triplet state of the ligand does not show any energy dependence in the studied energy range, interestingly a delayed formation of the triplet state occurs relative to the quantum dots decay. Based on the energetic dependence of triplet energy transfer we also suggest design criteria for future materials systems where triplet excitons from organic semiconductors are harvested via QDs, for instance in light emitting structures or the harvesting of triplet excitons generated via singlet fission.
关键词： singlet fission,quantum dots,solar energy,photon multiplication,triplet energy transfer
更新于2025-09-23 15:19:57
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Catalytic deracemization of chiral allenes by sensitized excitation with visible light
摘要： Chiral compounds exist as enantiomers that are non-superimposable mirror images of each other. Owing to the importance of enantiomerically pure chiral compounds—for example, as active pharmaceutical ingredients—separation of racemates (1:1 mixtures of enantiomers) is extensively performed. Frequently, however, only a single enantiomeric form of a chiral compound is required, which raises the question of how a racemate can be selectively converted into a single enantiomer. Such a deracemization process is entropically disfavoured and cannot be performed by a conventional catalyst in solution. Here we show that it is possible to photochemically deracemize chiral compounds with high enantioselectivity using irradiation with visible light (wavelength of 420 nanometres) in the presence of catalytic quantities (2.5 mole per cent) of a chiral sensitizer. We converted an array of 17 chiral racemic allenes into the respective single enantiomers with 89 to 97 per cent enantiomeric excess. The sensitizer is postulated to operate by triplet energy transfer to the allene, with different energy-transfer efficiencies for the two enantiomers. It thus serves as a unidirectional catalyst that converts one enantiomer but not the other, and the decrease in entropy is compensated by light energy. Photochemical deracemization enables the direct formation of enantiopure materials from a racemic mixture of the same compound, providing a novel approach to the challenge of creating asymmetry.
关键词： chiral sensitizer,triplet energy transfer,deracemization,chiral compounds,visible light,enantiomers,photochemical
更新于2025-09-04 15:30:14