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Synthesis, characterization, structural and photophysical properties of heteroleptic ruthenium complexes containing 2-(1H-benzo[d]imidazol-2-yl)quinoline ligand towards electrocatalytic CO2 reduction

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Abstract

Two novel mononuclear heteroleptic Ru(II) photosensitizers with 2-(1H-benzo[d]imidazol-2-yl)quinoline derivatives were designed and successfully synthesized. The facile synthesis and their photophysical properties are investigated. Both the Ru(II) complexes i.e., [RuII(bpy)2(L1)](ClO4) : [1](ClO4) and [RuII(bpy)2(L2)](ClO4)2 : [2](ClO4)2 {L1 = 2-(1H-benzo[d]imidazol-2-yl)quinoline and L2 = 2-(1-methyl-1H-benzo[d]imidazol-2-yl)quinoline} have been meticulously characterized by different spectroscopic and analytical techniques such as FT–IR, 1H NMR, ESI mass spectra, UV–vis and fluorescence spectroscopy, etc. Molecular structures of [1](ClO4) and [2](ClO4)2 have been determined by a single-crystal X-ray structure diffraction study. Redox and spectral properties of the synthesized Ru(II) complexes were examined along with their corresponding ligands and compared with the classic homoleptic [RuII(bpy)3](PF6)2. The effects on substituents in the ligand backbone were scrutinised. The emission behaviour of both [1](ClO4) and [2](ClO4)2 revealed relatively long-lived emissive 3MLCT and bathochromic shift (~ 715 nm) while compared with [RuII(bpy)3](PF6)2 (~ 605 nm). Fairly weak quantum yields for [1](ClO4) and [2](ClO4)2 : ∼ 0.00299 and ∼ 0.00295 with half-lives 181.57 ns and 198.89 ns, respectively, suggested different non-radiative emission pathways. Additionally, for [1](ClO4) and [2](ClO4)2, electrochemical reduction of carbon dioxide (CO2) in dry acetonitrile solvent was performed and showed great promises for future designing of electrochemical reduction of CO2.

Graphical abstract

Two mononuclear heteroleptic Ru(II) photosensitizers [1](ClO4) and [2](ClO4)2 containing 2-(1H-benzo[d]imidazol-2-yl)quinoline ligand were synthesized and investigated via FT–IR, 1H NMR, ESI mass spectra, UV–vis, time-resolved photoluminescence spectroscopy, X-ray structure, etc. Both [1](ClO4) and [2](ClO4)2 showed great promises for electrochemical reduction of carbon dioxide in dry acetonitrile.

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Acknowledgements

Financial support received from SERB, project no. ECR/2016/000382 (fellowship to S.K.), Council of Scientific and Industrial Research (CSIR) (fellowship to B.G., A.M. and K.S.) and IIT Hyderabad are gratefully acknowledged for the financial support.

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  1. Department of Chemistry, Indian Institute of Technology, Hyderabad, Kandi, Sangareddy, 502284, Telangana, India

    Sadananda Kumbhakar, Bishnubasu Giri, Arabinda Muley, Kalai Selvan Karumban & Somnath Maji

  2. Department of Physics, Indian Institute of Technology, Hyderabad, Kandi, Sangareddy, 502284, Telangana, India

    Chinmoy Biswas & Sai Santosh Kumar Raavi

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  1. Sadananda Kumbhakar
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Kumbhakar, S., Giri, B., Muley, A. et al. Synthesis, characterization, structural and photophysical properties of heteroleptic ruthenium complexes containing 2-(1H-benzo[d]imidazol-2-yl)quinoline ligand towards electrocatalytic CO2 reduction. J Chem Sci 134, 71 (2022). https://doi.org/10.1007/s12039-022-02063-z

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