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<p>The conformational looseness and recombination losses common to linear donor- π -acceptor (D- π -A) organic photovoltaics can be elegantly addressed by macrocyclic design methodologies. Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT) were used to extensively examine the effects of peripheral end-group engineering on a rigid arylborane-arylamine macrocyclic framework (MC1-R). Six novel metal-free derivatives (MC1-A1 to MC1-A6) were systematically produced by replacing the conventional terminal indanone-malononitrile (INCN) acceptor units with six distinct considerably electron-withdrawing end groups. Computational benchmarking at the MPW1PW91/6-31G(d, p) level in an implicit dichloromethane solvent environment successfully reproduced the experimental photophysical performance, leading to a minimal divergence of around 2&#xa0;nm in the expected absorption maxima (λmax). Peripheral modification disrupted the intrinsic symmetry of the parent macrocyclic framework, resulting in local redistribution of the frontier molecular orbitals (FMOs). In particular, the lowest unoccupied molecular orbital (LUMO) began to become increasingly dispersed among the peripheral acceptor units, whereas the highest occupied molecular orbital (HOMO) remained primarily contained within the central macrocyclic donor core. The fundamental electronic bandgap (Eg) reduces from 3.95&#xa0;eV (MC1-R) to 2.29&#xa0;eV (MC1-A1) by this spatial segregation. Consequently, there is a notable bathochromic shift of the absorption maximum (̛ƛmax) into the visible spectrum (535.96&#xa0;nm to 643.56&#xa0;nm). Furthermore, the proposed compounds successfully suppress geminate recombination with significantly higher ground-state total molecular dipole moments (µtot) up to 23.63 D and much lower exciton binding energies (Eb down to 0.34&#xa0;eV). Importantly, the series retains outstanding energy level matching and best-in-class theoretical open-circuit voltages (Voc up to 2.077&#xa0;V). MC1-A1 is the most notable non-fullerene acceptor among the evaluated candidates. Ultimately, this work develops robust structure-property criteria and emphasizes predictive quantum modeling as a crucial gatekeeper for rapid materials screening in high-performance organic solar cells.</p> Graphical abstract <p></p>

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Quantum chemical insights into end group-functionalized donor-π-acceptor non-fullerene materials for organic optoelectronics

  • 期刊论文

  • 发表日期：

    2026年8月1日

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  • Nimra Sultan,
  • Muhammad Ramzan Saeed Ashraf Janjua

摘要

The conformational looseness and recombination losses common to linear donor- π -acceptor (D- π -A) organic photovoltaics can be elegantly addressed by macrocyclic design methodologies. Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT) were used to extensively examine the effects of peripheral end-group engineering on a rigid arylborane-arylamine macrocyclic framework (MC1-R). Six novel metal-free derivatives (MC1-A1 to MC1-A6) were systematically produced by replacing the conventional terminal indanone-malononitrile (INCN) acceptor units with six distinct considerably electron-withdrawing end groups. Computational benchmarking at the MPW1PW91/6-31G(d, p) level in an implicit dichloromethane solvent environment successfully reproduced the experimental photophysical performance, leading to a minimal divergence of around 2 nm in the expected absorption maxima (λmax). Peripheral modification disrupted the intrinsic symmetry of the parent macrocyclic framework, resulting in local redistribution of the frontier molecular orbitals (FMOs). In particular, the lowest unoccupied molecular orbital (LUMO) began to become increasingly dispersed among the peripheral acceptor units, whereas the highest occupied molecular orbital (HOMO) remained primarily contained within the central macrocyclic donor core. The fundamental electronic bandgap (Eg) reduces from 3.95 eV (MC1-R) to 2.29 eV (MC1-A1) by this spatial segregation. Consequently, there is a notable bathochromic shift of the absorption maximum (̛ƛmax) into the visible spectrum (535.96 nm to 643.56 nm). Furthermore, the proposed compounds successfully suppress geminate recombination with significantly higher ground-state total molecular dipole moments (µtot) up to 23.63 D and much lower exciton binding energies (Eb down to 0.34 eV). Importantly, the series retains outstanding energy level matching and best-in-class theoretical open-circuit voltages (Voc up to 2.077 V). MC1-A1 is the most notable non-fullerene acceptor among the evaluated candidates. Ultimately, this work develops robust structure-property criteria and emphasizes predictive quantum modeling as a crucial gatekeeper for rapid materials screening in high-performance organic solar cells.

Graphical abstract