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Understanding pH Tailored Photophysical Properties of a \({\varvec{\pi}}\)-Conjugated Aryl Hydrazone-Derived Dye for Sensing Application

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Abstract

Time-dependent density functional theory implementing optimally-tuned range-separated hybrid combined with an appropriate solvent model is used to understand the pH-driven changes in the experimentally observed photophysical properties of a novel \(\pi \)-conjugated aryl hydrazone-derivative of dicyanomethylene-dihydro-trimethylfuran-carbonitrile (termed as DCDHF-H) dye in the polar solvent. Calculations reveal similar planar structures for the solvated ground and excited states of the DCDHF-H dye at low solution pH, leading to high fluorescence quantum yield. On the other hand, photoexcitation and subsequent charge-polarization triggered very fast excited-state nuclear relaxation of the deprotonated dye at high solution pH, producing a twisted structure from the planar ground state, which explains the observed fluorescence quenching. Only a small charge transfer is found at the solvated Franck-Condon and relaxed emissive state geometries. Importantly, the large electron-phonon couplings associated with the soft vibrational modes are found to open up nonradiative deactivation channels for the deprotonated form of the dye. Additionally, the presence of a low-lying triplet with remarkably high SOC between the \({S}_{1}\) and \({T}_{2}\) also opens up active nonradiative ISC channel only for the deprotonated dye, supporting the observed fluorescence switching off. These results are useful to understand the reported experimental observations better and provide valuable insights into designing small \(\pi \)-conjugated organic molecules for sensing and imaging applications.

Graphical Abstract

Rationales for the pH-triggered fluorescence switching in an aryl hydrazone-based dye in a polar solvent are provided using reliable quantum-chemical calculations.

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Acknowledgments

We gratefully acknowledge IIT Tirupati for providing the infrastructure and generous research support. AKM thanks DST-SERB (Grant No.: ECR/2017/001903) and DST-Inspire (Grant No.: DST/Inspire/04/2016/000137), Govt. of India for providing research grants.

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Authors and Affiliations

  1. Department of Chemistry and Center for Atomic, Molecular and Optical Sciences and Technologies, Indian Institute of Technology Tirupati, Tirupati, 517619, Andhra Pradesh, India

    Raka Ahmed & Arun K Manna

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  1. Raka Ahmed
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  2. Arun K Manna
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Correspondence to Arun K Manna.

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Dedicated to Professor S. P. Bhattacharyya on the occasion of his 75th birthday.

Special Issue on Interplay of Structure and Dynamics in Reaction Pathways, Chemical Reactivity and Biological Systems.

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Ahmed, R., Manna, A.K. Understanding pH Tailored Photophysical Properties of a \({\varvec{\pi}}\)-Conjugated Aryl Hydrazone-Derived Dye for Sensing Application. J Chem Sci 135, 9 (2023). https://doi.org/10.1007/s12039-022-02129-y

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  • DOI: https://doi.org/10.1007/s12039-022-02129-y

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