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Excited State and Non-linear Optical Properties of NIR Absorbing β-Thiophene-Fused BF2-Azadipyrromethene Dyes—Computational Investigation

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Abstract

Density functional theory and time-dependent density functional theory computations were used to understand the electronic and photophysical parameters of NIR β-thiophene-fused BF2-azadipyrromethene dyes. The computed data are in good agreement with those obtained experimentally and they provide insights into the origin of red shifted optical spectra compared to the parent aza-BODIPY, low Stokes shift, non-linear optical responses and quantitative description of the singlet–triplet energy gap. The resultant decrease in the HOMO − LUMO energy gap is responsible for the red shift. The possible use as non-linear optical materials is supported by large enhancement in the non-linear optical properties. On the basis of vertical triplet energies, their possible potential therapeutic use as a photosensitizer in photodynamic therapy is proposed. The singlet–triplet energetic gaps suggest that the β-thiophene-fused BF2-azadipyrromethene dyes can act as a sensitizer to produce an efficient generation of singlet oxygen. Their optimal use as an efficient singlet fission materials has been proposed on the basis of excitation energies in the ground, lowest singlet and triplet excited states.

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Acknowledgements

The authors Y. G. and N. S. greatly thankful to University Grant Commission-SAP, New Delhi, India for providing financial support.

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Authors and Affiliations

  1. Department of Dyestuff Technology, Institute of Chemical Technology, Nathalal Parekh Marg, Matunga, Mumbai, 400 019, India

    Yogesh Gawale & Nagaiyan Sekar

  2. Computational Chemistry Group, Department of Chemistry, Faculty of Science, University of Mauritius, Réduit, 80837, Mauritius

    Lydia Rhyman & Ponnadurai Ramasami

  3. Department of Applied Chemistry, University of Johannesburg, Doornfontein Campus, Johannesburg, 2028, South Africa

    Lydia Rhyman & Ponnadurai Ramasami

  4. Department of Chemical and Process Engineering, Jubail Industrial College, Jubail Industrial City, 31961, Saudi Arabia

    Mohamed I. Elzagheid

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  1. Yogesh Gawale
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  2. Lydia Rhyman
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  3. Mohamed I. Elzagheid
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  4. Ponnadurai Ramasami
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  5. Nagaiyan Sekar
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Correspondence to Ponnadurai Ramasami or Nagaiyan Sekar.

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Gawale, Y., Rhyman, L., Elzagheid, M.I. et al. Excited State and Non-linear Optical Properties of NIR Absorbing β-Thiophene-Fused BF2-Azadipyrromethene Dyes—Computational Investigation. J Fluoresc 28, 243–250 (2018). https://doi.org/10.1007/s10895-017-2186-z

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