The photophysics and cyclic voltammetry of two novel phosphorescent thiones, 2,2-dimethyl-indan-1-one-3-thione (DMIKT) and 2,2-dimethyl-indan-1,3-dithione (DMIDT), and three known phosphorescent thiones, 4H-pyran-4-thione (PT), 4H-1-benzopyran-4-thione (BPT) and 2,2-dimethylindan-1-thione (DMIT), have been characterised and compared. The phosphorescence emission of DMIT, DMIKT and DMIDT extends from the red into the near-IR spectral region. The additional carbonyl or thione group of DMIKT and DMIDT causes a significant shift in the emission maxima to 680 nm compared to that of DMIT, at 637 nm, in perfluorinated hydrocarbons. In acetonitrile the emission maxima of DMIKT and DMIDT are at 696 and 706 nm, respectively, and the spectra show vibronic bands which extend out beyond 850 nm. There is a significant reduction in triplet lifetime along this series (from 44 (±2) μs (DMIT) to 10 ((±0.8) μs (DMIKT) in perfluorinated solvents, and 8.6 (±0.5) (DMIT), 1.3 (±0.5) (DMIKT) and 0.35 (±0.07) μs (DMIDT) in acetonitrile), as well as a reduction in the rate constant for ground-state quenching of the triplet, (from 9.8 ((±0.9) to 3.5 ((±0.6) and 1.3 ((±0.2) × 109 mol−1 dm3 s−1 for the same compounds). The addition of the C=O or C=S groups also causes a decrease in phosphorescence quantum yield with the highest emission quantum yield obtained for DMIT (ΦP = 0.149 (±0.015)). Electrochemical studies show that while PT and BPT exhibit irreversible redox behaviour, DMIT, DMIKT and DMIDT all show at least one reversible reduction wave attributed to a one-electron process centred on the C=S moiety. The suitability of these lumophores for use in OLEDs is discussed.
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RCE would like to acknowledge the University of Wales Swansea (UWS) for provision of a research studentship and Kodak European R&D for financial support. Thanks are extended to Dr Chris P. Morley at Cardiff University for use of the cyclic voltammetry equipment and for useful discussion. Mass spectra were recorded by the EPSRC National Mass Spectrometry Centre located at UWS. Mr Ian Matthews (UWS) is acknowledged for technical support (NMR).
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