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The impact of phenyl–phenyl linkage on the thermodynamic, optical and morphological behavior of carbazol derivatives

The impact of structural differentiation between phenylcarbazoles (PhC, mCP, CBP, TCB) and phenylamines (TPA, BDB, TPB, TDAB) on the phase equilibria, optical spectrum, band gap, and thin-film morphology is evaluated and discussed. The carbazolyl units lead to a lower electronic conjugation contribu...

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Autores principales: Costa, José C. S., Lima, Marco A. L., Mendes, Adélio, Santos, Luís M. N. B. F.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9050612/
https://www.ncbi.nlm.nih.gov/pubmed/35496587
http://dx.doi.org/10.1039/d0ra01518k
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author Costa, José C. S.
Lima, Marco A. L.
Mendes, Adélio
Santos, Luís M. N. B. F.
author_facet Costa, José C. S.
Lima, Marco A. L.
Mendes, Adélio
Santos, Luís M. N. B. F.
author_sort Costa, José C. S.
collection PubMed
description The impact of structural differentiation between phenylcarbazoles (PhC, mCP, CBP, TCB) and phenylamines (TPA, BDB, TPB, TDAB) on the phase equilibria, optical spectrum, band gap, and thin-film morphology is evaluated and discussed. The carbazolyl units lead to a lower electronic conjugation contributing to a wide band gap when compared with the diphenylamine analogs. The fusion and sublimation equilibria indicate that entropic contribution is the key factor for the distinguished melting behavior and solid-phase volatility between phenylcarbazole derivatives and phenylamine analogs. The molecular differentiation between the two classes of compounds is not reflected in the crystal packing and intermolecular interactions. However, compared with the diphenylamino groups, the incorporation of carbazolyl moieties contributes to a less flexible molecule. Moreover, the results evidence that intermolecular bonding disruption along the fusion transition is more extensive for phenylamine derivatives. Due to the asymmetric nonplanar structure, mCP is characterized by a ratio of {T(g)/T(m) ≈ 3/4} while the more symmetric CBP and TCB molecules display ratios closer to {T(g)/T(m) ≈ 2/3}. Vapor-deposited thin films of mCP, CBP, and TCB are amorphous and their morphology is highly dependent on the substrate roughness. The lower flexibility of nonplanar phenylcarbazoles induces the formation of a glassy state due to the harder packing mechanism leading to the lower ability of the crystallization process.
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spelling pubmed-90506122022-04-29 The impact of phenyl–phenyl linkage on the thermodynamic, optical and morphological behavior of carbazol derivatives Costa, José C. S. Lima, Marco A. L. Mendes, Adélio Santos, Luís M. N. B. F. RSC Adv Chemistry The impact of structural differentiation between phenylcarbazoles (PhC, mCP, CBP, TCB) and phenylamines (TPA, BDB, TPB, TDAB) on the phase equilibria, optical spectrum, band gap, and thin-film morphology is evaluated and discussed. The carbazolyl units lead to a lower electronic conjugation contributing to a wide band gap when compared with the diphenylamine analogs. The fusion and sublimation equilibria indicate that entropic contribution is the key factor for the distinguished melting behavior and solid-phase volatility between phenylcarbazole derivatives and phenylamine analogs. The molecular differentiation between the two classes of compounds is not reflected in the crystal packing and intermolecular interactions. However, compared with the diphenylamino groups, the incorporation of carbazolyl moieties contributes to a less flexible molecule. Moreover, the results evidence that intermolecular bonding disruption along the fusion transition is more extensive for phenylamine derivatives. Due to the asymmetric nonplanar structure, mCP is characterized by a ratio of {T(g)/T(m) ≈ 3/4} while the more symmetric CBP and TCB molecules display ratios closer to {T(g)/T(m) ≈ 2/3}. Vapor-deposited thin films of mCP, CBP, and TCB are amorphous and their morphology is highly dependent on the substrate roughness. The lower flexibility of nonplanar phenylcarbazoles induces the formation of a glassy state due to the harder packing mechanism leading to the lower ability of the crystallization process. The Royal Society of Chemistry 2020-03-24 /pmc/articles/PMC9050612/ /pubmed/35496587 http://dx.doi.org/10.1039/d0ra01518k Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Costa, José C. S.
Lima, Marco A. L.
Mendes, Adélio
Santos, Luís M. N. B. F.
The impact of phenyl–phenyl linkage on the thermodynamic, optical and morphological behavior of carbazol derivatives
title The impact of phenyl–phenyl linkage on the thermodynamic, optical and morphological behavior of carbazol derivatives
title_full The impact of phenyl–phenyl linkage on the thermodynamic, optical and morphological behavior of carbazol derivatives
title_fullStr The impact of phenyl–phenyl linkage on the thermodynamic, optical and morphological behavior of carbazol derivatives
title_full_unstemmed The impact of phenyl–phenyl linkage on the thermodynamic, optical and morphological behavior of carbazol derivatives
title_short The impact of phenyl–phenyl linkage on the thermodynamic, optical and morphological behavior of carbazol derivatives
title_sort impact of phenyl–phenyl linkage on the thermodynamic, optical and morphological behavior of carbazol derivatives
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9050612/
https://www.ncbi.nlm.nih.gov/pubmed/35496587
http://dx.doi.org/10.1039/d0ra01518k
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