Tuning the Electronic Properties of a Nitro- and Cyano-Functionalized Benzothienoquinolizinium Salt as Potential Organic N-Type Semiconductor: Experimental and Theoretical Study

Aracena, Andrés; Wrighton-Araneda, Kerry; Pezet, Katherine; Vilches, Diego; Angel, Felipe A.; Chandía, Ihan; Zúñiga, César; Elgueta, Sebastián; González, Javiera

doi:10.3390/cryst16090575

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Tuning the Electronic Properties of a Nitro- and Cyano-Functionalized Benzothienoquinolizinium Salt as Potential Organic N-Type Semiconductor: Experimental and Theoretical Study

by

Andrés Aracena

^1,2,*

,

Kerry Wrighton-Araneda

^3,4,

Katherine Pezet

⁵,

Diego Vilches

⁶

,

Felipe A. Angel

^6,7,8

,

Ihan Chandía

¹,

César Zúñiga

^1,2,

Sebastián Elgueta

⁹

and

Javiera González

¹

Instituto de Ciencias Naturales, Facultad de Medicina Veterinaria y Agronomia, Universidad de Las Americas, Sede Santiago (Campus Providencia), Avenida Manuel Montt 948, Providencia 7500000, Chile

²

Centro de Investigacion en Ciencias Biologicas y Quimicas, Universidad de Las Americas, Avenida Manuel Montt 948, Providencia 7500000, Chile

³

Escuela de Kinesiología/Facultad de Ciencias de la Salud, Universidad Bernardo OHiggins, Santiago 8320000, Chile

⁴

Centro Integrativo de Biología y Química Aplicada (CIBQA), Universidad Bernardo OHiggins, Santiago 8320000, Chile

⁵

Departamento de Química, Facultad de Ciencias Naturales, Matemáticas y Medio Ambiente, Universidad Tecnológica Metropolitana (UTEM), J. P. Alessandri 1242, Ñuñoa 7800002, Chile

⁶

Departamento de Química Inorgánica, Escuela de Química, Facultad de Química y de Farmacia, Pontificia Universidad Católica de Chile, Santiago 7820436, Chile

⁷

Centro de Nanotecnología y Materiales Avanzados, CIEN-UC, Pontificia Universidad Católica de Chile, Santiago 7820436, Chile

⁸

Centro de Energía, CE-UC, Pontificia Universidad Católica de Chile, Santiago 7820436, Chile

⁹

Escuela de Nutricion y Dietetica, Facultad de Ciencias de la Rehabilitacion y Calidad de Vida, Universidad San Sebastian, Providencia 7500000, Chile

^*

Author to whom correspondence should be addressed.

Crystals 2026, 16(9), 575; https://doi.org/10.3390/cryst16090575

Submission received: 18 July 2026 / Revised: 21 August 2026 / Accepted: 30 August 2026 / Published: 2 September 2026

(This article belongs to the Special Issue Advances in Optoelectronic Materials)

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Abstract

A new nitro- and cyano-functionalized, tetradecyl-substituted benzothienoquinolizinium tetrafluoroborate was synthesized through oxidative photocyclisation of a pyridinium precursor and evaluated as a potential small molecule N-type organic semiconductor. The precursor and the photocyclised salts were characterized by UV–Vis absorption spectroscopy, DSC, ¹H and ¹³C NMR, and cyclic voltammetry. Their optoelectronic properties were further investigated by DFT and TD-DFT calculations. Photocyclisation induced a marked bathochromic extension of the absorption profile, decreasing the optical band gap from 3.19 eV for the pyridinium precursor to 2.61 eV for the fused benzothienoquinolizinium salt. Cyclic voltammetry revealed a stabilized electrochemical LUMO level of approximately −3.87 eV, supporting the electron-deficient character of the nitro/cyano-substituted cationic scaffold. Frontier molecular orbital analysis showed that the HOMO and LUMO are mainly localized on the fused π-conjugated core and electron-withdrawing aryl substituents, with negligible contribution from the tetradecyl chain and BF₄⁻ counterion. TD-DFT and electron excitation analyses indicated that the monomeric low-energy transition has mixed local/charge-transfer character, whereas π-stacked dimers, especially the face-to-face arrangement, enhance charge transfer character and reduce electron–hole Coulombic attraction. Marcus type charge transport calculations revealed packing dependent behavior, with the face-to-face dimer displaying nearly ambipolar transport with a slight electron preference. A preliminary theoretical donor–acceptor model with hexaphenyl-substituted hexabenzocoronene further suggested energetic compatibility and strong intermolecular charge-transfer character. Overall, these results identify this benzothienoquinolizinium tetrafluoroborate as a promising electron-deficient cationic π-scaffold for future organic optoelectronic materials.

Keywords: organic electronics; organic N-type semiconductors; non-fullerene acceptors

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MDPI and ACS Style

Aracena, A.; Wrighton-Araneda, K.; Pezet, K.; Vilches, D.; Angel, F.A.; Chandía, I.; Zúñiga, C.; Elgueta, S.; González, J. Tuning the Electronic Properties of a Nitro- and Cyano-Functionalized Benzothienoquinolizinium Salt as Potential Organic N-Type Semiconductor: Experimental and Theoretical Study. Crystals 2026, 16, 575. https://doi.org/10.3390/cryst16090575

AMA Style

Aracena A, Wrighton-Araneda K, Pezet K, Vilches D, Angel FA, Chandía I, Zúñiga C, Elgueta S, González J. Tuning the Electronic Properties of a Nitro- and Cyano-Functionalized Benzothienoquinolizinium Salt as Potential Organic N-Type Semiconductor: Experimental and Theoretical Study. Crystals. 2026; 16(9):575. https://doi.org/10.3390/cryst16090575

Chicago/Turabian Style

Aracena, Andrés, Kerry Wrighton-Araneda, Katherine Pezet, Diego Vilches, Felipe A. Angel, Ihan Chandía, César Zúñiga, Sebastián Elgueta, and Javiera González. 2026. "Tuning the Electronic Properties of a Nitro- and Cyano-Functionalized Benzothienoquinolizinium Salt as Potential Organic N-Type Semiconductor: Experimental and Theoretical Study" Crystals 16, no. 9: 575. https://doi.org/10.3390/cryst16090575

APA Style

Aracena, A., Wrighton-Araneda, K., Pezet, K., Vilches, D., Angel, F. A., Chandía, I., Zúñiga, C., Elgueta, S., & González, J. (2026). Tuning the Electronic Properties of a Nitro- and Cyano-Functionalized Benzothienoquinolizinium Salt as Potential Organic N-Type Semiconductor: Experimental and Theoretical Study. Crystals, 16(9), 575. https://doi.org/10.3390/cryst16090575

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Tuning the Electronic Properties of a Nitro- and Cyano-Functionalized Benzothienoquinolizinium Salt as Potential Organic N-Type Semiconductor: Experimental and Theoretical Study

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