HJ-aggregates of donor–acceptor–donor oligomers and polymers

Chang, Xin; Balooch Qarai, Mohammad; Spano, Frank C.

doi:10.1063/5.0054877

Title: HJ-aggregates of donor–acceptor–donor oligomers and polymers

Journal Article · Mon Jul 19 00:00:00 EDT 2021 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0054877· OSTI ID:1853427

Chang, Xin ^[1];

^[1];

^[1]

Temple University, Philadelphia, PA (United States)

A vibronic exciton model is developed to account for the spectral signatures of HJ-aggregates of oligomers and polymers containing donor–acceptor–donor (DAD) repeat units. In (DAD)_N π-stacks, J-aggregate-promoting intrachain interactions compete with H-aggregate promoting interchain interactions. The latter includes Coulombic coupling, which arises from “side-by-side” fragment transition dipole moments as well as intermolecular charge transfer (ICT), which is enhanced in geometries with substantial overlap between donors on one chain and acceptors on a neighboring chain. J-behavior is dominant in single (DAD)N chains with enhanced intrachain order as evidenced by an increased red-shift in the low-energy absorption band along with a heightened A₁/A₂ peak ratio, where A₁ and A₂ are the oscillator strengths of the first two vibronic peaks in the progression sourced by the symmetric quinoidal–aromatic vibration. By contrast, the positive H-promoting interchain Coulomb interactions operative in aggregates cause the vibronic ratio to attenuate, similar to what has been established in H-aggregates of homopolymers such as P3HT. An attenuated A₁/A₂ ratio can also be caused by H-promoting ICT which occurs when the electron and hole transfer integrals are out-of-phase. In this case, the A₁ peak is red-shifted, in contrast to conventional Kasha H-aggregates. With slight modifications, the ratio formula derived previously for P3HT aggregates is shown to apply to (DAD)_N aggregates as well, allowing one to determine the effective free-exciton interchain coupling from the A₁/A₂ ratio. Applications are made to polymers based on 2T-DPP-2T and 2T-BT-2T repeat units, where the importance of the admixture of the excited acceptor state in the lowest energy band is emphasized.

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Research Organization:: Univ. of Washington, Seattle, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0020046

OSTI ID:: 1853427

Journal Information:: Journal of Chemical Physics, Vol. 155, Issue 3; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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