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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...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
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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. |
format | Online Article Text |
id | pubmed-9050612 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
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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