{"title":"腙衍生物分子开关的光致异构化机理研究。","authors":"Xiaojuan Pang, Kaiyue Zhao, Chenghao Yang, Quanjie Zhong, Ningbo Zhang, Chenwei Jiang","doi":"10.1021/acsomega.5c00820","DOIUrl":null,"url":null,"abstract":"<p><p>Improving quantum yield is an important characteristic for enhancing the operational efficiency of light-driven molecular motors. Building upon Cigan et al.'s pioneering work on CH<sub>3</sub> substitution for H (RSC Adv., 2015, 5, 62449), we have developed a structural modification strategy for hydrazone-based molecular switches through the replacement of a single oxygen atom with two hydrogen atoms, resulting in a remarkable enhancement of the quantum yield. We systematically investigate the photoinduced isomerization mechanism of the hydrazone derivatives molecular switch using the Tully's surface hopping method on the semiempirical OM2/MRCI level. The results show that the calculated quantum yield for the E-to-Z photoisomerization of this molecular rotary motor is approximately (55 ± 3)% (16.01% for original (Pang, X.-J.; Zhao, K.-Y.; He, H.-Y.; Zhang, N.-B.; Jiang, C.-W. Photoinduced isomerization mechanism of isatin N<sup>2</sup>-diphenylhydrazones molecular switch. Acta Phys. Sin. 2024, 73 (17).) with an average lifetime of the excited state of 122 fs. Additionally, we calculate the time-dependent fluorescence emission spectra and observe a redshift in wavelength accompanied by fluorescence emission quenching, which shows a blue shift compared to the original isatin N<sup>2</sup>-diphenylhydrazone spectrum. Furthermore, we propose that this molecular switch may not have a \"dark state\".</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 17","pages":"17898-17906"},"PeriodicalIF":4.3000,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12059938/pdf/","citationCount":"0","resultStr":"{\"title\":\"Study on the Photoinduced Isomerization Mechanism of Hydrazone Derivatives Molecular Switch.\",\"authors\":\"Xiaojuan Pang, Kaiyue Zhao, Chenghao Yang, Quanjie Zhong, Ningbo Zhang, Chenwei Jiang\",\"doi\":\"10.1021/acsomega.5c00820\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Improving quantum yield is an important characteristic for enhancing the operational efficiency of light-driven molecular motors. Building upon Cigan et al.'s pioneering work on CH<sub>3</sub> substitution for H (RSC Adv., 2015, 5, 62449), we have developed a structural modification strategy for hydrazone-based molecular switches through the replacement of a single oxygen atom with two hydrogen atoms, resulting in a remarkable enhancement of the quantum yield. We systematically investigate the photoinduced isomerization mechanism of the hydrazone derivatives molecular switch using the Tully's surface hopping method on the semiempirical OM2/MRCI level. The results show that the calculated quantum yield for the E-to-Z photoisomerization of this molecular rotary motor is approximately (55 ± 3)% (16.01% for original (Pang, X.-J.; Zhao, K.-Y.; He, H.-Y.; Zhang, N.-B.; Jiang, C.-W. Photoinduced isomerization mechanism of isatin N<sup>2</sup>-diphenylhydrazones molecular switch. Acta Phys. Sin. 2024, 73 (17).) with an average lifetime of the excited state of 122 fs. Additionally, we calculate the time-dependent fluorescence emission spectra and observe a redshift in wavelength accompanied by fluorescence emission quenching, which shows a blue shift compared to the original isatin N<sup>2</sup>-diphenylhydrazone spectrum. Furthermore, we propose that this molecular switch may not have a \\\"dark state\\\".</p>\",\"PeriodicalId\":22,\"journal\":{\"name\":\"ACS Omega\",\"volume\":\"10 17\",\"pages\":\"17898-17906\"},\"PeriodicalIF\":4.3000,\"publicationDate\":\"2025-04-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12059938/pdf/\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Omega\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acsomega.5c00820\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2025/5/6 0:00:00\",\"PubModel\":\"eCollection\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Omega","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acsomega.5c00820","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/5/6 0:00:00","PubModel":"eCollection","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Study on the Photoinduced Isomerization Mechanism of Hydrazone Derivatives Molecular Switch.
Improving quantum yield is an important characteristic for enhancing the operational efficiency of light-driven molecular motors. Building upon Cigan et al.'s pioneering work on CH3 substitution for H (RSC Adv., 2015, 5, 62449), we have developed a structural modification strategy for hydrazone-based molecular switches through the replacement of a single oxygen atom with two hydrogen atoms, resulting in a remarkable enhancement of the quantum yield. We systematically investigate the photoinduced isomerization mechanism of the hydrazone derivatives molecular switch using the Tully's surface hopping method on the semiempirical OM2/MRCI level. The results show that the calculated quantum yield for the E-to-Z photoisomerization of this molecular rotary motor is approximately (55 ± 3)% (16.01% for original (Pang, X.-J.; Zhao, K.-Y.; He, H.-Y.; Zhang, N.-B.; Jiang, C.-W. Photoinduced isomerization mechanism of isatin N2-diphenylhydrazones molecular switch. Acta Phys. Sin. 2024, 73 (17).) with an average lifetime of the excited state of 122 fs. Additionally, we calculate the time-dependent fluorescence emission spectra and observe a redshift in wavelength accompanied by fluorescence emission quenching, which shows a blue shift compared to the original isatin N2-diphenylhydrazone spectrum. Furthermore, we propose that this molecular switch may not have a "dark state".
ACS OmegaChemical Engineering-General Chemical Engineering
CiteScore
6.60
自引率
4.90%
发文量
3945
审稿时长
2.4 months
期刊介绍:
ACS Omega is an open-access global publication for scientific articles that describe new findings in chemistry and interfacing areas of science, without any perceived evaluation of immediate impact.