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Dimeric conformation sensitive electronic excited states of tetracene congeners and their unconventional non-fluorescent behaviour

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Abstract

Unconventional non-fluorescent J-aggregates of Tetracene (TC) and Naphtho[2,1,8-qra]tetracene (NT) were witnessed and their consequent dramatic quenching was unravelled by a steady state, time-resolved and transient spectroscopy in conjunction with excited state density functional calculations. The TC O-aggregate with slippage angle \(\uptheta = 22.3^{\circ }< 54.7^{\circ }\) exhibited substantial transition dipole moment (TDM) for both lower (2.79 D) and higher (1.59 D) energy singlet excitations, while, NT formed an ideal J-aggregate (polarization angle, \(\upalpha \sim 0^{\circ })\) with a predominant TDM to only a lower excitonic state (2.69 D). Subsequently, their unusual quenching was quantified with large drops in the photoluminescence quantum yields (PLQY) from 0.116 to 0.002 upon TC O-aggregation and from 0.478 to 0.038 upon NT J-aggregation. These intense PL drops were systematically investigated for possible occurrence of excimer-like emission quenching and/or photo-degradation of the TC core unit. In view of the TC O-aggregates exhibiting a perfect energetic balance between the singlet (2.34 eV) and triplet (1.28 eV) energies for singlet fission (SF) and a concomitant delayed fluorescence signal, their \(\hbox {S}_{{1}}\) decay characteristics were attributed to SF followed by an inverse triplet-triplet recombination. In contrast, the energetic imbalance (\(\hbox {E}(\hbox {S}_{1}) < \hbox {2xE}(\hbox {T}_{1})\)) in NT J-aggregates permitted only forward process of SF and the resulting long-lived triplet formation was traced with a positive transient absorption (\(\hbox {T}_{1} \rightarrow \hbox {T}_{\mathrm{n}})\) band at 500 nm. Accordingly, the singlet excited state \((\hbox {S}_{1})\) dynamics of TC O- and NT J-aggregates, being largely dominated by SF, depicted a depleted \(\hbox {S}_{{1}}\) population, accounting for the large deviation from aggregation induced enhanced emission, exhibited by classical dye J-aggregates.

Graphical Abstract:

Unconventional O- and J -aggregates of Tetracene and Naphtho[2,1,8-qra]tetracene showed non-fluorescent behaviour whose singlet excited state (S\(_{1})\) dynamics was largely governed by fast Singlet Fission decay, accounting for atypical deviation from the well-established aggregation induced enhanced emission from classical J-aggregates.

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Acknowledgements

N. A. thanks CSIR, New Delhi, for a Research Fellowship. P. G. Senapathy centre for computing resources, Sophisticated Analytical Instrumental Facility (SAIF) and Department of Chemical Engineering, IIT-Madras, are gratefully acknowledged for providing excellent Computing, TCSPC and HRSEM facilities. Grateful thanks are due to Dr. Soumya, Laser Flash Photolysis Laboratory at IIT-Madras for carrying out the nanosecond Flash Photolysis experiments. The authors thank CSIR, New Delhi, India, Grant no. 01(2830)/15/EMR-II for financial support.

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  1. N Aggarwal

    Present address: Department of Chemistry and Biochemistry, Sharda University, Greater Noida, Uttar Pradesh, 201 310, India

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  1. Colloids and Interface Chemistry Laboratory, Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600 036, India

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Aggarwal, N., Patnaik, A. Dimeric conformation sensitive electronic excited states of tetracene congeners and their unconventional non-fluorescent behaviour. J Chem Sci 131, 52 (2019). https://doi.org/10.1007/s12039-019-1626-5

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