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Study of excited state relaxation by time-resolved spectroscopy in conjugated substituted polyene bis-oxazoles

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Abstract

The simultaneous quantum-chemical and spectral investigations of the possible relaxation pathways in the excited state for the two α,ω-di-substituted polyenes were performed. Lengthening of the polymethine chain is accompanied by the considerable decreasing of the first electron transition and hence is manifested as the bathochromic shift of both absorption and fluorescence spectra; however, the nature of transition does not change. It is established that the considerable changes of the bond lengths in polymethine chain for both vinylogs in the excited state cause firstly the appearance of the fast component in short wavelengths spectral region; after relaxation, the intensity of the fast component decreases, and it disappears, but then the spectral band, shifted bathochromically, appears, so that its maximum coincide with the band maximum in the steady-state fluorescence maximum, what corresponds to the final symmetrical relaxation of bond lengths. The parallel quantum-chemical calculation shows that two highest levels are mainly formed by the donor levels of both terminal groups and hence twice occupied splitting levels. Upon excitation, one of the splitting MO (HOMO) becomes single occupied; this causes the molecule in the excited state to be unstable and could transform it to the unsymmetrical form. Such relaxation path is confirmed by the time-resolved spectra: the spectral band in both molecules, with the different polymethine chains, undergoes the subsequent bathochromical shifting.

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Authors and Affiliations

  1. Faculty of Physics, Taras Shevchenko National University of Kyiv, 60 Volodymirska Str, Kyiv, 03127, Ukraine

    K. Maiko & I. Dmitruk

  2. Institute of High Technologies, Taras Shevchenko National University of Kyiv, 4-g, Glushkova Str, Kyiv, 02033, Ukraine

    D. Merzhyievskyi

  3. Institute of Physics NAS of Ukraine, 46 Nauki Ave, Kyiv, 03039, Ukraine

    Yu. Piryatinski

  4. O.O. Bogomolets National Medical University, 13 T. Shevchenko Blvd, Kyiv, 01601, Ukraine

    N. Obernikhina

  5. V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry, NAS of Ukraine, 1 Murmanska St, Kyiv, 02660, Ukraine

    O. Shablykin, Ya. Prostota, O. Kachkovsky & V. Brovarets

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  1. K. Maiko
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  2. D. Merzhyievskyi
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  3. Yu. Piryatinski
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  4. N. Obernikhina
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  5. O. Shablykin
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  8. O. Kachkovsky
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Contributions

O. Kachkovsky performed the ideas, formulation of overarching research goals and aims, and development of methodology. V. Brovarets performed the ideas and management and coordination responsibility for the research activity planning and execution. N. Obernikhina performed the formulation of research goals and aims and application of statistical, mathematical, computational, or other formal techniques to analyze study data. O. Shablykin performed the evolution of research goals and aims and application of formal techniques to analyze and synthesize study data. D. Merzhyievskyi performed the design of methodology in synthesis and creation of models and proof and analysis of their structure. Ya. Prostota performed the design of methodology in synthesis and creation of models, proof, and analysis of their structure. I. Dmitruk performed the design of methodology in spectral measurements, creation of models, and analysis of results time-resolved spectroscopy. Yu. Piryatinski performed the conducting spectral measurements and investigation process, specifically performing the time-resolved spectroscopy and data/evidence collection. K. Maiko performed the preparation, creation, and presentation of the published work.

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Correspondence to O. Kachkovsky.

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Maiko, K., Merzhyievskyi, D., Piryatinski, Y. et al. Study of excited state relaxation by time-resolved spectroscopy in conjugated substituted polyene bis-oxazoles. Struct Chem 32, 977–987 (2021). https://doi.org/10.1007/s11224-021-01752-8

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