Applying strong external electric field to thiophene‐based oligomers: A promising approach to upgrade semiconducting performance

Xie

et al. 2020

J. Phys. Chem. Lett.

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An intuitive design strategy for organic semiconductors with ultrasmall reorganization energy (λ) is proposed. Learning from a total of 98 molecules condensed by benzene and/or thiophene rings, we find that linear compounds in D 2h symmetry have the smallest λ in each of the three molecular categories (PAHs, thienothiophenes, benzothiophenes). 2D expanded analogues that contain these D 2h building blocks also give unusually small λ (<100 meV). λ of 1D elongated polycyclics show an approximate linear correlation with the ring-averaged HOMA indices and the HOMO–LUMO gaps. Compared to the symmetry principle, the HOMA and energy gap, though much less intuitive to design a priori, provide additional quantitative guidelines to further optimize λ through substitutions, for example, when molecules have the same symmetries. Our results indicate that ring-fused π-conjugates that have narrower HOMO–LUMO gaps and are less aromatic are better candidates to achieve ultrasmall λ.

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confidence: 93%

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confidence: 99%

Designing Organic Semiconductors with Ultrasmall Reorganization Energies: Insights from Molecular Symmetry, Aromaticity and Energy Gap

Xie

et al. 2020

J. Phys. Chem. Lett.

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J of Physical Organic Chem

“…21 Zhan et al conducted a detailed theoretical investigation on the effect of EEF on typical oligothiophenes to upgrade semiconducting performance with the help of EEF. 22 Stuyver et al reported that EEF induces shortening or lengthening of chemical bonds and can modulate chemical reactions and further reported that EEF is a potential commonly applicable "zapping" tool to facilitate elaborate chemical syntheses. 23 Moreover, several studies reported that molecules exhibit changes under the action of EEF, such as change in chemical bond, molecular charge distribution, energy, dipole moment, Raman, and infrared intensity.…”

Section: Introductionmentioning

confidence: 99%

“…González‐Henríquez et al explored the resonance effect on conductivity of polyesters containing thiophene and silarene after polarization under EEF and reported that the arrangement of dipoles increased electrical conductivity 21 . Zhan et al conducted a detailed theoretical investigation on the effect of EEF on typical oligothiophenes to upgrade semiconducting performance with the help of EEF 22 . Stuyver et al reported that EEF induces shortening or lengthening of chemical bonds and can modulate chemical reactions and further reported that EEF is a potential commonly applicable “zapping” tool to facilitate elaborate chemical syntheses 23 .…”

Section: Introductionmentioning

confidence: 99%

Influence of external electric field on structure, spectra and various properties of 3‐Chlorothieno[2,3‐b]pyridine‐2‐carbonitrile using density functional theory

Tao

et al. 2023

Thiophene and pyridine compounds are widely used in medicine, pesticides, and material fields, and study of their physical and chemical changes under an external electric field (EEF) will improve a deep understanding of their properties. In this work, we selected 3‐Chlorothieno[2,3‐b]pyridine‐2‐carbonitrile (CPC) as the representative and explored the structure, total energy, dipole moment, Hirshfeld charge, molecular electrostatic potential, infrared, Raman, and UV‐Vis spectra of CPC under EEF through density functional theory (DFT). The calculations indicated that the bond length, the bond angle, total energy, dipole moment, and energy gap of CPC are strongly affected by EEF. Infrared, Raman, and UV‐Vis spectra showed stark vibration effects with increasing EFF. Our results provide a basis for further applications of CPC with and without EEF.

“…23 In addition to molecular packing, another environmental factor that is often overlooked is the external electric field (EEF). 24 In a typical field-effect transistor, the EEF can be generated by the electrodes, and the gate voltage controls the channel conductivity. To a reasonable approximation, the field strength (F) at the semiconductor−insulator interface is expressed as F = F i (k i / k s ), 25 where F i is the field strength felt in the insulator, and k i and k s are the dielectric constants respectively for the insulator and the semiconductor.…”

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confidence: 99%

Electric-Field Effects on the Internal Charge Reorganization Energies of Crystalline Organic Semiconductors

Wang,

He,

et al. 2023

J. Phys. Chem. Lett.

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The synergistic effects of molecular packing and external electric fields (EEFs, including axial and nonaxial fields) on the internal charge reorganization energies (λ) of typical p-type SMOS have been investigated. Combined quantum and molecular mechanics calculations show that, for all-ring-fused rigid molecules singlemolecule approximation and neglect of EEFs are adequate for computing λ, while for nonrigid molecules with inter-ring carbon−carbon (IRCC) linkers, the above simplifications may cause a significant deviation from the actual λ. For nonrigid molecules, solid-state packing can prevent "bad" EEFs (F z and F yz ) from enhancing λ (adverse to charge transfer), while it allows λ to be greatly reduced (in favor of charge transfer) if "good" EEFs (F x , F xy , F xz and F xyz ) are imposed. Last, a simple strategy that can divide λ into each subring contribution for IRCC-linked molecules has been proposed.