Conformational Control and Charge Separation Dynamics in Perylene Bisimide-based Donor-Acceptor Polymers

Abstract

The development of organic electronic materials is fundamentally influenced by the electronic structure of π-conjugated polymers. Precise positioning of donor and acceptor (D-A) units plays a crucial role in tailoring electronic properties to meet desired requirements. In this study, we report the synthesis and investigation of a novel class of D-A polymers. Four polymers, two with hanging and two with linear configurations of perylene bisimide, were designed and synthesized using Hay-Glaser and oxidative coupling polymerization methods. These polymers differ in the length of the saturated spacer connecting a bithiophene, thiophene-acetylene “donor” core to a bay-substituted perylene bisimide “acceptor”. Femtosecond transient absorption spectroscopy enabled the correlation of the variations in charge separation and stabilization with conformational preferences and the folding behavior of the polymers. AFM images show that the polymer forms a maximum chain length of up to ~175 nm (up to ~140 monomers) and self-assembles on the hexagonal graphite lattice with a distinct threefold orientation. Notably, this study establishes a direct correlation between molecular conformation (linear vs. hanging configurations) and optoelectronic properties, deepening the understanding of how spatial orientation influences charge separation and stabilization dynamics.

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BibTeX

@misc{veer2026conformational,
  title = {{Conformational Control and Charge Separation Dynamics in Perylene Bisimide-based Donor-Acceptor Polymers}},
  author = {Sairam Dnyaneshwar Veer and Chandragopal Thanasekar and Nitika Kharbanda and Tanmay Goswami and Nidhi Rawat and Sunny M. P. Gautam and Himanshu Bhatt and Ipsita Parichha and Abdulla and Aswini Narayanan and Michael Moos and Christoph Lambert and Hirendra N. Ghosh and Thiruvancheril G. Gopakumar and Sukumaran Santhosh Babu and Narayanan and Santhosh Sukumaran},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010602/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010602/v1},
  note = {CC BY},
}

RIS

TY  - UNPB
TI  - Conformational Control and Charge Separation Dynamics in Perylene Bisimide-based Donor-Acceptor Polymers
AU  - Sairam Dnyaneshwar Veer
AU  - Chandragopal Thanasekar
AU  - Nitika Kharbanda
AU  - Tanmay Goswami
AU  - Nidhi Rawat
AU  - Sunny M. P. Gautam
AU  - Himanshu Bhatt
AU  - Ipsita Parichha
AU  - Abdulla
AU  - Aswini Narayanan
AU  - Michael Moos
AU  - Christoph Lambert
AU  - Hirendra N. Ghosh
AU  - Thiruvancheril G. Gopakumar
AU  - Sukumaran Santhosh Babu
AU  - Narayanan
AU  - Santhosh Sukumaran
PY  - 2026
DA  - 2026/10/16
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010602/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010602/v1
AB  - The development of organic electronic materials is fundamentally influenced by the electronic structure of π-conjugated polymers. Precise positioning of donor and acceptor (D-A) units plays a crucial role in tailoring electronic properties to meet desired requirements. In this study, we report the synthesis and investigation of a novel class of D-A polymers. Four polymers, two with hanging and two with linear configurations of perylene bisimide, were designed and synthesized using Hay-Glaser and oxidative coupling polymerization methods. These polymers differ in the length of the saturated spacer connecting a bithiophene, thiophene-acetylene “donor” core to a bay-substituted perylene bisimide “acceptor”. Femtosecond transient absorption spectroscopy enabled the correlation of the variations in charge separation and stabilization with conformational preferences and the folding behavior of the polymers. AFM images show that the polymer forms a maximum chain length of up to ~175 nm (up to ~140 monomers) and self-assembles on the hexagonal graphite lattice with a distinct threefold orientation. Notably, this study establishes a direct correlation between molecular conformation (linear vs. hanging configurations) and optoelectronic properties, deepening the understanding of how spatial orientation influences charge separation and stabilization dynamics.
ER  -

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