Computational and Crystallographic Examination of Naphthoquinone Based Diarylethene Photochromes
Photochromic compounds have a lengthy history of study and a profusion of applications that stand to gain from these studies. Among the classes of photochromic compounds, diarylethenes show desirable properties including high fatigue resistance and thermal stability, thus meeting some of the most im...
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doaj-72cf0044d7744344b117330ee069f40d2020-11-25T02:35:59ZengMDPI AGMolecules1420-30492020-06-01252630263010.3390/molecules25112630Computational and Crystallographic Examination of Naphthoquinone Based Diarylethene PhotochromesDinesh G. Patel0Martial Boggio-Pasqua1Travis B. Mitchell2Ian M. Walton3William R. Quigley4Frank A. Novak5Department of Chemistry, the Pennsylvania State University at Hazleton, Hazleton, PA 18202, USALaboratoire de Chimie et Physique Quantiques, CNRS/Université Paul Sabatier, 31062 Toulouse, FranceDepartment of Chemistry, the State University of New York at Buffalo, Buffalo, NY 14260-3000, USADepartment of Chemistry, the State University of New York at Buffalo, Buffalo, NY 14260-3000, USADepartment of Chemistry, the Pennsylvania State University at Hazleton, Hazleton, PA 18202, USADepartment of Chemistry, the Pennsylvania State University at Hazleton, Hazleton, PA 18202, USAPhotochromic compounds have a lengthy history of study and a profusion of applications that stand to gain from these studies. Among the classes of photochromic compounds, diarylethenes show desirable properties including high fatigue resistance and thermal stability, thus meeting some of the most important criteria necessary to enter the realm of practical applications. Recently, photochromic diarylethenes containing quinone functionalities have demonstrated interesting optical and solid-state properties. When properly interfaced with suitable electron withdrawing groups on the aryl component, both the ring-opening and ring-closing reactions can be achieved with visible light; this is in contrast to most other diarylethenes where UV light is required for ring closure. Unfortunately, quantitative conversion from open to closed forms is not possible. In this work, we examine the relative energies of conformations of solid-state structures observed by X-ray crystallography and evaluate their thermal stabilities based on density functional theory (DFT) calculations. Time-dependent DFT (TD–DFT) is used to model the UV-vis absorption spectra of these quinone diarylethenes. We show that spectral overlap between open and closed forms is a major hindrance to full photoconversion.https://www.mdpi.com/1420-3049/25/11/2630diarylethenesphotochromesquinonesTD–DFT computations |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Dinesh G. Patel Martial Boggio-Pasqua Travis B. Mitchell Ian M. Walton William R. Quigley Frank A. Novak |
spellingShingle |
Dinesh G. Patel Martial Boggio-Pasqua Travis B. Mitchell Ian M. Walton William R. Quigley Frank A. Novak Computational and Crystallographic Examination of Naphthoquinone Based Diarylethene Photochromes Molecules diarylethenes photochromes quinones TD–DFT computations |
author_facet |
Dinesh G. Patel Martial Boggio-Pasqua Travis B. Mitchell Ian M. Walton William R. Quigley Frank A. Novak |
author_sort |
Dinesh G. Patel |
title |
Computational and Crystallographic Examination of Naphthoquinone Based Diarylethene Photochromes |
title_short |
Computational and Crystallographic Examination of Naphthoquinone Based Diarylethene Photochromes |
title_full |
Computational and Crystallographic Examination of Naphthoquinone Based Diarylethene Photochromes |
title_fullStr |
Computational and Crystallographic Examination of Naphthoquinone Based Diarylethene Photochromes |
title_full_unstemmed |
Computational and Crystallographic Examination of Naphthoquinone Based Diarylethene Photochromes |
title_sort |
computational and crystallographic examination of naphthoquinone based diarylethene photochromes |
publisher |
MDPI AG |
series |
Molecules |
issn |
1420-3049 |
publishDate |
2020-06-01 |
description |
Photochromic compounds have a lengthy history of study and a profusion of applications that stand to gain from these studies. Among the classes of photochromic compounds, diarylethenes show desirable properties including high fatigue resistance and thermal stability, thus meeting some of the most important criteria necessary to enter the realm of practical applications. Recently, photochromic diarylethenes containing quinone functionalities have demonstrated interesting optical and solid-state properties. When properly interfaced with suitable electron withdrawing groups on the aryl component, both the ring-opening and ring-closing reactions can be achieved with visible light; this is in contrast to most other diarylethenes where UV light is required for ring closure. Unfortunately, quantitative conversion from open to closed forms is not possible. In this work, we examine the relative energies of conformations of solid-state structures observed by X-ray crystallography and evaluate their thermal stabilities based on density functional theory (DFT) calculations. Time-dependent DFT (TD–DFT) is used to model the UV-vis absorption spectra of these quinone diarylethenes. We show that spectral overlap between open and closed forms is a major hindrance to full photoconversion. |
topic |
diarylethenes photochromes quinones TD–DFT computations |
url |
https://www.mdpi.com/1420-3049/25/11/2630 |
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