Modulating Exciton Dynamics Through Fluorescent Side Group Incorporation in Benzodithiophene-Benzotriazole-Isoindigo Terpolymers

Hauyón, René; Pérez, Yasmín; Zúñiga, Daniela; Araya, Scarlet; Camacho, Bastian; Thomas, Pablo; Saldías, Cesar; Fuentealba, Denis; Terraza, Claudio A.; Angel, Felipe A.; Jessop, Ignacio A.

doi:10.3390/polym18121554

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Modulating Exciton Dynamics Through Fluorescent Side Group Incorporation in Benzodithiophene-Benzotriazole-Isoindigo Terpolymers

by

René Hauyón

¹

,

Yasmín Pérez

²,

Daniela Zúñiga

²,

Scarlet Araya

²,

Bastian Camacho

²,

Pablo Thomas

²,

Cesar Saldías

^1,3

,

Denis Fuentealba

¹

,

Claudio A. Terraza

^1,3

,

Felipe A. Angel

^1,3,4

and

Ignacio A. Jessop

^2,*

¹

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

²

Organic and Polymeric Materials Research Laboratory, Facultad de Ciencias, Universidad de Tarapacá, Arica 1000007, Chile

³

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

⁴

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

^*

Author to whom correspondence should be addressed.

Polymers 2026, 18(12), 1554; https://doi.org/10.3390/polym18121554 (registering DOI)

Submission received: 25 May 2026 / Revised: 8 June 2026 / Accepted: 20 June 2026 / Published: 22 June 2026

(This article belongs to the Section Polymer Chemistry)

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Abstract

In this work, we investigated the incorporation of a fluorescent side group, fluorescein octyl ester (FOE), in benzodithiophene-based donor–acceptor terpolymers as a strategy to modulate excited-state behavior. Three FOE-containing terpolymers (P2-iIa-c), obtained at different polymerization times, were systematically evaluated against an analogous material without the fluorescent pendant unit (P1-iI). Thermal analysis revealed good thermal stability and an increase in glass transition temperature upon FOE incorporation, suggesting restricted segmental mobility and increased conformational constraints within the conjugated backbone. Optical characterization showed distinct absorption spectra with reaction time and shorter fluorescence lifetimes for the FOE-containing materials, consistent with the presence of additional excited-state deactivation pathways and intramolecular energy transfer processes within the terpolymer backbone. An approximate estimation of energy transfer efficiencies (≈60–65%) suggested that such processes may be operative within the system. Cyclic voltammetry measurements showed only minor variations in HOMO and LUMO energy levels between P1-iI and P2-iIa-c series, indicating that the conjugated backbone predominantly determined the frontier orbital energies despite side chain modification. Furthermore, photocurrent measurements from the bilayer device configuration exhibited a systematic increase in photocurrent for the FOE-containing material, supporting the role of excitonic modulation, rather than significant changes in interfacial energetic alignment. These results suggest that fluorescent side chain incorporation provides an effective strategy for regulating exciton dynamics while maintaining the electronic structure of the donor–acceptor terpolymer.

Keywords: π-conjugated terpolymers; fluorescent side groups; intramolecular FRET; exciton dynamics

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MDPI and ACS Style

Hauyón, R.; Pérez, Y.; Zúñiga, D.; Araya, S.; Camacho, B.; Thomas, P.; Saldías, C.; Fuentealba, D.; Terraza, C.A.; Angel, F.A.; et al. Modulating Exciton Dynamics Through Fluorescent Side Group Incorporation in Benzodithiophene-Benzotriazole-Isoindigo Terpolymers. Polymers 2026, 18, 1554. https://doi.org/10.3390/polym18121554

AMA Style

Hauyón R, Pérez Y, Zúñiga D, Araya S, Camacho B, Thomas P, Saldías C, Fuentealba D, Terraza CA, Angel FA, et al. Modulating Exciton Dynamics Through Fluorescent Side Group Incorporation in Benzodithiophene-Benzotriazole-Isoindigo Terpolymers. Polymers. 2026; 18(12):1554. https://doi.org/10.3390/polym18121554

Chicago/Turabian Style

Hauyón, René, Yasmín Pérez, Daniela Zúñiga, Scarlet Araya, Bastian Camacho, Pablo Thomas, Cesar Saldías, Denis Fuentealba, Claudio A. Terraza, Felipe A. Angel, and et al. 2026. "Modulating Exciton Dynamics Through Fluorescent Side Group Incorporation in Benzodithiophene-Benzotriazole-Isoindigo Terpolymers" Polymers 18, no. 12: 1554. https://doi.org/10.3390/polym18121554

APA Style

Hauyón, R., Pérez, Y., Zúñiga, D., Araya, S., Camacho, B., Thomas, P., Saldías, C., Fuentealba, D., Terraza, C. A., Angel, F. A., & Jessop, I. A. (2026). Modulating Exciton Dynamics Through Fluorescent Side Group Incorporation in Benzodithiophene-Benzotriazole-Isoindigo Terpolymers. Polymers, 18(12), 1554. https://doi.org/10.3390/polym18121554

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Modulating Exciton Dynamics Through Fluorescent Side Group Incorporation in Benzodithiophene-Benzotriazole-Isoindigo Terpolymers

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