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Exploration of photophysics of 2,2’-pyridil at room temperature and 77 K: a combined spectroscopic and quantum chemical approach

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Abstract

The photophysics of 2,2’-pyridil has been explored thoroughly using steady state and time resolved fluorometric techniques at room temperature (RT) in liquid media as well as in glassy matrices at cryogenic temperature (77 K). Ethanol and methylcyclohexane are exploited for this purpose, as polar and non-polar media respectively. Notwithstanding the observation of multiple emissions from the fluorophore, the experiments unequivocally rule out emission from excited singlet states other than the S1 state, consistent with Kasha’s rule. Among 1,2-dicarbonyl molecular systems, this behavior resembles that of a-furil, while it contradicts that of benzil and a-naphthil which exhibit S2 emissions. The dual fluorescence and dual phosphorescence of the fluorophore are ascribed to the emissions originating from the two conformers, namely near-trans and relaxed skew. Coexistence of the two conformers is substantiated by time resolved area normalized emission spectroscopy (TRANES) at both RT and 77 K. The potential energy curves (PECs) simulated from calculations based on density functional theory and its time dependent extension provide adequate support to the experimental observations.

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  1. Department of Chemistry, Jadavpur University, Kolkata-700032, India

    Pronab Kundu, Saptarshi Ghosh & Nitin Chattopadhyay

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  1. Pronab Kundu
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  2. Saptarshi Ghosh
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Correspondence to Nitin Chattopadhyay.

Additional information

Electronic supplementary information (ESI) available: Fluorescence excitation spectra of 2,2’-pyridil monitored at different wavelengths over the entire emission band in both EtOH and MCH solvents upon photoexcitation at the np* absorption band, room temperature emission and excitation spectra of 2,2’-pyridil in ethanol at different time windows, the phosphorescence decays of 2,2’-pyridil in EtOH and MCH frozen matrices at various monitoring wavelengths at 77 K upon photoexcitation at np* and pp* absorption bands, potential energy curves of different electronic states (S0, S1, S2, S3 and T1) of 2,2’-pyridil in vacuum, table collecting the relevant phosphorescence lifetime data and table collecting experimental and calculated absorption wavelengths in EtOH and MCH.

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Kundu, P., Ghosh, S. & Chattopadhyay, N. Exploration of photophysics of 2,2’-pyridil at room temperature and 77 K: a combined spectroscopic and quantum chemical approach. Photochem Photobiol Sci 16, 159–169 (2017). https://doi.org/10.1039/c6pp00378h

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