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Abstract The application potential of singlet fission (SF), describing the spontaneous conversion of an excited singlet into two triplets, underlines the necessity to independently control SF rates, energetics and the optical band gap. Heterofission, whereby the singlet splits into triplets on chemically distinct chromophores, is a promising approach to control the above-mentioned parameters, but its details are not yet fully understood. Here, we investigate the photophysics of blends of two prototypical SF chromophores, tetracene (TET) and rubrene (RUB) using time-resolved photoluminescence spectroscopy and time-correlated single photon counting to explore the potential for heterofission in combinations of endothermic SF chromophores. 

Abstract The fission of singlet excitons into triplet pairs in organic materials holds great technological promise, but the rational application of this phenomenon is hampered by a lack of understanding of its complex photophysics. Here, we use the controlled introduction of vacancies by means of spacer molecules in tetracene and pentacene thin films as a tuning parameter complementing experimental observables to identify the operating principles of different singlet fission pathways. Time-resolved spectroscopic measurements in combination with microscopic modelling enables us to demonstrate distinct scenarios, resulting from different singlet-to-triplet pair energy alignments. For pentacene, where fission is exothermic, coherent mixing between the photoexcited singlet and triplet-pair states is promoted by vibronic resonances, which drives the fission process with little sensitivity to the vacancy concentration. Such vibronic resonances do not occur for endothermic materials such as tetracene, for which we find fission to be fully incoherent; a process that is shown to slow down with increasing vacancy concentration. 

Sulfur oxidation state is used to tune organic room temperature phosphorescence (RTP) of symmetric sulfur-bridged carbazole dimers. The sulfide-bridged compound exhibits a factor of 3 enhancement of the phosphorescence efficiency, compared to the sulfoxide and sulfone-bridged analogs, despite sulfone bridges being commonly used in RTP materials. In order to investigate the origin of this enhancement, temperature dependent spectroscopy measurements and theoretical calculations are used. The RTP lifetimes are similar due to similar crystal packing modes. Computational studies reveal that the lone pairs on the sulfur atom have a profound impact on enhancing intersystem crossing rate through orbital mixing and screening, which we hypothesize is the dominant factor responsible for increasing the phosphorescence efficiency. The ability to tune the electronic state without altering crystal packing modes allows the isolation of these effects. This work provides a new perspective on the design principles of organic phosphorescent materials, going beyond the rules established for conjugated ketone/sulfone-based organic molecules.