Study of the Heterocyclic-Substituted Platinum-1,2-Enedithiolate 3ILCT Excited States by Transient Absorption Spectroscopy

Abstract

The photoluminescent 1,2-enedithiolate complexes, (dppe)Pt{S2C2(2-quinoxaline)(H)}, [L2Pt{S2C2(2-pyridinium)(H)}]+ where L2 = dppm and dppe, [L2Pt{S2C2(4-pyridinium)(H)}]+, [L2Pt{2C2(N-Methyl-4-pyridinium)(H)}]+ and [L2Pt{S2C2(CH2CH2-N-2-pyridinium)}]+ where L2 = dppm, dppe, and dppp are room temperature dual emitters where the emissions have thiolate to heterocycle π* intraligand charge transfer character (ILCT) singlet and triplet character. The pyridinium complexes have strong triplet-triplet absorption bands at approximately 400, 520 and 630 nm with a weaker band at 800 nm while (dppe)Pt{S2C2(2-quinoxaline)(H)} has strong triplet-triplet absorption bands at 385 and 550 nm with weaker bands at 610 and 805 nm. By fitting the decay of the transients to single exponential kinetics, the 3ILCT* lifetimes of the pyridinium complexes where determined to be 0.7 to 15.9 μs (DMSO) while the 3ILCT* lifetime of (dppe)Pt{S2C2(2-quinoxaline)(H)} was determined to be 2.8 μs (CH3CN). The transient absorption spectra of the complexes is affected by the appended heterocycle rather than the bulk of ancillary phosphine ligand or whether the heterocycle is protonated or alkylated.

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Van Houten, K.A., Walters, K.A., Schanze, K.S. et al. Study of the Heterocyclic-Substituted Platinum-1,2-Enedithiolate 3ILCT Excited States by Transient Absorption Spectroscopy. Journal of Fluorescence 10, 35–40 (2000). https://doi.org/10.1023/A:1009483512750

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  • Transient absorption
  • platinum-1,2-enedithiolates
  • dual emitter
  • pyridinyl radical