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Phenothiazine functionalized fulleropyrrolidines: synthesis, charge transport and applications to organic solar cells

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A series of phenothiazine-C60/70 dyads containing fulleropyrrolidine tethered to C-3 position (C60-PTZ and C70-PTZ) or to the heteroatom N-position via either phenyl (C60-Ph–PTZ and C70-Ph-PTZ) or phenoxyethyl linkers (C60-PhOEt-PTZ and C70-PhOEt-PTZ) of the phenothiazine were synthesized and light-induced electron transfer events were explored. Optimized studies suggested that the highest molecular orbital (HOMO) resides on donor phenothiazine moiety while lowest molecular orbital (LUMO) on the acceptor fulleropyrrolidine moiety of the dyads. Optical and electrochemical properties suggested no electronic communication between the donor and acceptor moieties in the ground state. However, steady-state emission studies in solvents of varied polarity, involving selective excitation of C60/C70, disclosed that the emission intensity of C60/C70 was quenched in the dyads in the increasing order, C60/70-PTZ > C60/70-Ph-PTZ > C60/70-PhOEt-PTZ as a consequence of the donor–acceptor distance resulted due to spacer lengths. Also, the emission quenching is more pronounced in polar solvents such as DMF compared to a non-polar solvent, toluene. With the support of parallel electrochemical studies, the emission quenching is attributed to intramolecular photo-induced electron transfer occurring from PTZ to (C60/C70)* generating a radical ion pair, PTZ+⋅–C60−⋅/PTZ+⋅–C70−⋅. Finally, bulk heterojunction (BHJ) solar cells devices inverted fashion prepared by employing the dyads as acceptors, and PTB7 as donor, suggested that the devices prepared from C70 derivatives i.e., PTB7:C70-PTZ and PTB7:C70-PhOEt-PTZ exhibited better power conversion efficiency of 2.66% and 2.15%, respectively over C60 derivatives i.e., PTB7:C60-PTZ and PTB7:C60-PhOEt-PTZ with the efficiencies of 1.80 and 1.72%, respectively. AFM studies revealed that the poor performance of PTB7:C60-PTZ- and PTB7:C60-PhOEt-PTZ-based devices can be ascribed to the lower solubility of the dyads in 1,2-DCB solvent leading to rough morphology.

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Acknowledgements

Author RC is grateful to Department of Science and Technology (DST, CRG/2018/002661), and also DST-FIST grants, SR/FST/CSi-257/2014(C) and SR/FST/CSII/2018/65 awarded to Department of Chemistry, Central University of Rajasthan and Department of Chemistry, National Institute of Technology Warangal for the financial support of this work. The authors LG is grateful to Department of Science and Technology (DST, SB/S1/IC-14/2014), for the financial support. The authors RP is grateful to Department of Science and Technology (DST, ECR/2018/002346, EEQ/2019/000656). Author DB acknowledges Council of Scientific and Industrial Research (CSIR) for Senior Research Fellowship and Pooja acknowledges NITW for the Research Fellowship. We thank the Director CSIR-IICT for support (IICT/Pubs./2022/142).

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Authors and Affiliations

  1. Department of Chemistry, School of Chemical Sciences and Pharmacy, Central University of Rajasthan, Kishangarh, Ajmer, Rajasthan, 305817, India

    Deepak Badgurjar, Sapna Gahlot & Raghu Chitta

  2. Polymers and Functional Materials Division, CSIR-Indian Institute of Chemical Technology, Tarnaka, Hyderabad, Telangana, 500007, India

    Naresh Duvva, Anirban Bagui, Surya Prakash Singh & Lingamallu Giribabu

  3. Department of Chemistry, National Institute of Technology Warangal, Hanamkonda, Warangal, Telangana, 506004, India

    Pooja, Ravinder Pawar & Raghu Chitta

  4. Academy of Scientific and Innovative Research, Ghaziabad, 201002, India

    Surya Prakash Singh & Lingamallu Giribabu

  5. Department of Sustainable Energy Engineering, Indian Institute of Technology Kanpur, Kanpur, India

    Ashish Garg

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  1. Deepak Badgurjar
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  9. Lingamallu Giribabu
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Correspondence to Lingamallu Giribabu or Raghu Chitta.

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Badgurjar, D., Duvva, N., Bagui, A. et al. Phenothiazine functionalized fulleropyrrolidines: synthesis, charge transport and applications to organic solar cells. Photochem Photobiol Sci 22, 379–393 (2023). https://doi.org/10.1007/s43630-022-00322-z

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