{"title":"Dihydro-1H-Pyrazoles as Donor Blocks in Donor–Acceptor Chromophores for Electro-Optics: A DFT Study of Hyperpolaizability and Electronic Excitations","authors":"Roman Ishchenko, Vladimir Shelkovnikov","doi":"10.1002/qua.27511","DOIUrl":null,"url":null,"abstract":"<div>\n \n <p>A diverse set of promising donors for donor–acceptor chromophores based on dihydro-1<i>H</i>-pyrazole (pyrazoline) for use in electro-optics was investigated using DFT at M06-2X/aug-cc-pVDZ level of theory. These calculations showed that it is possible to achieve a molecular hyperpolarizability of up to 1700*10<sup>−30</sup> esu (up to three times higher compared to conventional diethylaniline donors) for a simple tricyanofuran-based acceptor by carefully tuning the donor structure. It was shown that the molecular hyperpolarizability is mainly affected by the substituents in the aryl rings in positions 3 and 1 of the pyrazoline cycle, while the substituents of the aryl ring in position 5 and the pyrazoline ring itself can be varied without significant effects on the hyperpolarizability. For one of the compounds, a detailed study of the lowest energy electronic excitation was performed using the TD-DFT, confirming the role of the pyrazoline ring as a secondary donor.</p>\n </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":null,"pages":null},"PeriodicalIF":2.3000,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"International Journal of Quantum Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/qua.27511","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
A diverse set of promising donors for donor–acceptor chromophores based on dihydro-1H-pyrazole (pyrazoline) for use in electro-optics was investigated using DFT at M06-2X/aug-cc-pVDZ level of theory. These calculations showed that it is possible to achieve a molecular hyperpolarizability of up to 1700*10−30 esu (up to three times higher compared to conventional diethylaniline donors) for a simple tricyanofuran-based acceptor by carefully tuning the donor structure. It was shown that the molecular hyperpolarizability is mainly affected by the substituents in the aryl rings in positions 3 and 1 of the pyrazoline cycle, while the substituents of the aryl ring in position 5 and the pyrazoline ring itself can be varied without significant effects on the hyperpolarizability. For one of the compounds, a detailed study of the lowest energy electronic excitation was performed using the TD-DFT, confirming the role of the pyrazoline ring as a secondary donor.
期刊介绍:
Since its first formulation quantum chemistry has provided the conceptual and terminological framework necessary to understand atoms, molecules and the condensed matter. Over the past decades synergistic advances in the methodological developments, software and hardware have transformed quantum chemistry in a truly interdisciplinary science that has expanded beyond its traditional core of molecular sciences to fields as diverse as chemistry and catalysis, biophysics, nanotechnology and material science.