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Delineating the effect of substituent and π-bridge flip on the photophysical properties of pyrene derivatives: answers from DFT/TD-DFT calculations

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Abstract

Pyrene-based Schiff base derivatives have attracted enormous potential as fluorescent probe for multifarious research applications due to their fashionable photophysical properties. In the present work, pyrene-based Schiff base derivatives of 4-[(pyren-1-ylmethylene)amino]phenol (PAP1-12) were computationally designed with hydroxyl (–OH) substitution at different positions on phenyl rings and have been studied using density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. All the designed molecules were found to possess a coplanar geometry. PAP1-6 molecules with the phenol moiety substituted on the nitrogen atom of the C=N π-bridge were found to possess relatively small dipole moment values than PAP7-12 with phenol moiety substituted on the carbon atom of the C=N bridge that is flipped. Frontier molecular orbital (FMO) analysis divulged that HOMO to LUMO transition in PAP1-6 molecules is of π → π* character signifying that these molecules are potential aggregation-induced emission (AIE) molecules while PAP7-12 showed ICT character in correspondence with the order witnessed in dipole moment values. With regard to the HOMO–LUMO energy gap, PAP4 was estimated to show relatively small value than other molecules and as a result it exhibited the largest absorption maxima of 425 nm and large first hyperpolarizability value of 40 × 10–30 esu. On the other hand, PAP6 molecule possessed relatively larger emission λmax value of around 500 nm. In essence, the present work demonstrates that change in the substituents on the PAP derivatives and the flipping of C=N π-bridge rendered PAP1-6 suitable for AIE application and PAP7-12 for ICT application. This substituent dependency and effect of π-bridge flipping could be capitalized upon for future development of similar organic dyes for diverse applications.

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Acknowledgements

MJ sincerely acknowledges the Department of Science and Technology (DST), New Delhi, India, for the financial support provided through DST-Inspire Faculty award (Ref. No. IFA13-CH-100). Authors also thank the Loyola College Management and Director, Loyola Institute of Frontier Energy (LIFE), Loyola College, Chennai, for the infrastructural support to carry out the research work.

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Authors and Affiliations

  1. Department of Chemistry and Computational Chemistry Laboratory, Loyola Institute of Frontier Energy, Loyola College, Chennai, Tamil Nadu, 600 034, India

    Murugesan Panneerselvam, Neethinathan Johnee Britto, Shanmugam Murali Krishnan & Madhavan Jaccob

  2. Department of Chemistry, Vel Tech Rangarajan Dr Sagunthala R & D Institute of Science and Technology, Avadi, Chennai, Tamil Nadu, 600 062, India

    Arunkumar Kathiravan

  3. Institute of Inorganic Chemistry, University of Heidelberg, Heidelberg, Germany

    Gunasekaran Velmurugan

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  1. Murugesan Panneerselvam
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  2. Arunkumar Kathiravan
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  3. Neethinathan Johnee Britto
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  4. Shanmugam Murali Krishnan
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  5. Gunasekaran Velmurugan
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  6. Madhavan Jaccob
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Correspondence to Gunasekaran Velmurugan or Madhavan Jaccob.

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Handling Editor: M. Grant Norton.

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Supplementary Information

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10853_2022_7095_MOESM1_ESM.docx

Supplementary file1 (DOCX 4751 kb) Optimized structures of selected pyrene-based Schiff bases in the gas phase obtained at the PBE0/6-311+G(d,p) level of theory, electron density distribution of HOMOs and LUMOs of selected pyrene-based Schiff bases in the gas phase obtained at the PEB0/6-311+G(d,p) level of theory, calculated frontier molecular orbital contribution of PAP derivatives

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Panneerselvam, M., Kathiravan, A., Johnee Britto, N. et al. Delineating the effect of substituent and π-bridge flip on the photophysical properties of pyrene derivatives: answers from DFT/TD-DFT calculations. J Mater Sci 57, 10724–10735 (2022). https://doi.org/10.1007/s10853-022-07095-x

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  • DOI: https://doi.org/10.1007/s10853-022-07095-x

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