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Viable access to the triplet excited state in peryleneimide based palladium complex\(^{\S }\)

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Abstract

Triplet excited state in organic chromophores is ubiquitously significant owing to its utility in light harvesting and photovoltaic device applications. Herein, we report the enhancement in the triplet character of an innately triplet deficient peryleneimide chromophore via incorporation of a heavy atom. Palladium incorporated perylenemonoimide (PMI-Pd) was synthesized via oxidative addition of PMI-Br into Pd(0) under inert experimental conditions. The structural sanctity of the PMI-Pd and the model derivative PMI was characterized via single crystal X-ray diffraction and the close-packing was examined employing Hirshfeld surface analysis. The steady-state spectroscopic measurements of PMI-Pd in chloroform reveal an apparent perturbation in the UV-Vis absorption, fluorescence emission and lifetime characteristics. A much higher perturbation is observed in the ultrafast photoexcited processes of PMI-Pd in chloroform as envisaged via nanosecond transient absorption (nTA) measurements. The nTA measurements of PMI-Pd in chloroform reveal a significant enhancement in the triplet character of PMI-Pd as compared to the model derivative PMI. Spin-orbit coupling (SOC) mediated triplet enhancement in PMI-Pd suggest heavy atom incorporation as a viable route for accessing the triplet excited states in triplet deficient aromatic chromophores. SOC mediated triplet enhancement in innately triplet deficient organic chromophores can revive the utility of these materials for novel photovoltaic and energy storage applications.

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SYNOPSIS Synthesis and characterization of a perylenemonoimide palladium(II) complex (PMI-Pd) and the enhancement in the triplet excited state of PMI-Pd as compared to PMI are explored. The results suggest that the combined spin-orbit coupling mediated by the incorporation of palladium and bromine atoms results in the enhancement of the triplet character in PMI-Pd.

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Acknowledgements

M. H. acknowledges Kerala State Council for Science, Technology and Environment (KSCSTE) for the support of this work, 007/KSYSA-RG/2014/KSCSTE. The authors thank A. P. Andrews, IISER-TVM for the single crystal X-ray structure analyses. A.M.P., G.G., E.S. & R.R. thank IISER-TVM, and Department of Science and Technology (DST) INSPIRE, University Grant Commission (UGC) fellowships for the financial assistance.

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  1. School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram (IISER-TVM), Maruthamala P.O., Vithura, Thiruvananthapuram, Kerala, 695 551, India

    Abbey M Philip, Ebin Sebastian, Gopika Gopan, Remya Ramakrishnan & Mahesh Hariharan

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Correspondence to Mahesh Hariharan.

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$$^{\S }$$ § Dedicated to Professor M V George on the occasion of his $$90^{{\mathrm{th}}}$$ 90 th Birth Anniversary.

Special Issue on Photochemistry, Photophysics and Photobiology

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Philip, A.M., Sebastian, E., Gopan, G. et al. Viable access to the triplet excited state in peryleneimide based palladium complex\(^{\S }\). J Chem Sci 130, 137 (2018). https://doi.org/10.1007/s12039-018-1537-x

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  • DOI: https://doi.org/10.1007/s12039-018-1537-x

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