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Ambipolar Charge Transport in Organic Semiconductors: How Intramolecular Reorganization Energy Is Controlled by Diradical Character

The charged forms of π–conjugated chromophores are relevant in the field of organic electronics as charge carriers in optoelectronic devices, but also as energy storage substrates in organic batteries. In this context, intramolecular reorganization energy plays an important role in controlling mater...

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Detalles Bibliográficos
Autores principales: Dai, Yasi, Zerbini, Andrea, Casado, Juan, Negri, Fabrizia
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10304932/
https://www.ncbi.nlm.nih.gov/pubmed/37375198
http://dx.doi.org/10.3390/molecules28124642
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author Dai, Yasi
Zerbini, Andrea
Casado, Juan
Negri, Fabrizia
author_facet Dai, Yasi
Zerbini, Andrea
Casado, Juan
Negri, Fabrizia
author_sort Dai, Yasi
collection PubMed
description The charged forms of π–conjugated chromophores are relevant in the field of organic electronics as charge carriers in optoelectronic devices, but also as energy storage substrates in organic batteries. In this context, intramolecular reorganization energy plays an important role in controlling material efficiency. In this work, we investigate how the diradical character influences the reorganization energies of holes and electrons by considering a library of diradicaloid chromophores. We determine the reorganization energies with the four-point adiabatic potential method using quantum–chemical calculations at density functional theory (DFT) level. To assess the role of diradical character, we compare the results obtained, assuming both closed-shell and open-shell representations of the neutral species. The study shows how the diradical character impacts the geometrical and electronic structure of neutral species, which in turn control the magnitude of reorganization energies for both charge carriers. Based on computed geometries of neutral and charged species, we propose a simple scheme to rationalize the small, computed reorganization energies for both n-type and p-type charge transport. The study is supplemented with the calculation of intermolecular electronic couplings governing charge transport for selected diradicals, further supporting the ambipolar character of the investigated diradicals.
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spelling pubmed-103049322023-06-29 Ambipolar Charge Transport in Organic Semiconductors: How Intramolecular Reorganization Energy Is Controlled by Diradical Character Dai, Yasi Zerbini, Andrea Casado, Juan Negri, Fabrizia Molecules Article The charged forms of π–conjugated chromophores are relevant in the field of organic electronics as charge carriers in optoelectronic devices, but also as energy storage substrates in organic batteries. In this context, intramolecular reorganization energy plays an important role in controlling material efficiency. In this work, we investigate how the diradical character influences the reorganization energies of holes and electrons by considering a library of diradicaloid chromophores. We determine the reorganization energies with the four-point adiabatic potential method using quantum–chemical calculations at density functional theory (DFT) level. To assess the role of diradical character, we compare the results obtained, assuming both closed-shell and open-shell representations of the neutral species. The study shows how the diradical character impacts the geometrical and electronic structure of neutral species, which in turn control the magnitude of reorganization energies for both charge carriers. Based on computed geometries of neutral and charged species, we propose a simple scheme to rationalize the small, computed reorganization energies for both n-type and p-type charge transport. The study is supplemented with the calculation of intermolecular electronic couplings governing charge transport for selected diradicals, further supporting the ambipolar character of the investigated diradicals. MDPI 2023-06-08 /pmc/articles/PMC10304932/ /pubmed/37375198 http://dx.doi.org/10.3390/molecules28124642 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Dai, Yasi
Zerbini, Andrea
Casado, Juan
Negri, Fabrizia
Ambipolar Charge Transport in Organic Semiconductors: How Intramolecular Reorganization Energy Is Controlled by Diradical Character
title Ambipolar Charge Transport in Organic Semiconductors: How Intramolecular Reorganization Energy Is Controlled by Diradical Character
title_full Ambipolar Charge Transport in Organic Semiconductors: How Intramolecular Reorganization Energy Is Controlled by Diradical Character
title_fullStr Ambipolar Charge Transport in Organic Semiconductors: How Intramolecular Reorganization Energy Is Controlled by Diradical Character
title_full_unstemmed Ambipolar Charge Transport in Organic Semiconductors: How Intramolecular Reorganization Energy Is Controlled by Diradical Character
title_short Ambipolar Charge Transport in Organic Semiconductors: How Intramolecular Reorganization Energy Is Controlled by Diradical Character
title_sort ambipolar charge transport in organic semiconductors: how intramolecular reorganization energy is controlled by diradical character
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10304932/
https://www.ncbi.nlm.nih.gov/pubmed/37375198
http://dx.doi.org/10.3390/molecules28124642
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