{"title":"二芳烯正式1,2-各向异性重排的能量分布","authors":"E. K. Kouame, A. G. Lvov","doi":"10.21285/2227-2925-2022-12-1-153-159","DOIUrl":null,"url":null,"abstract":"Diarylethenes with thiophene substituents belong to photoswitchable compounds (photoswitches or photochromes). Upon UV irradiation, their colorless open-ring isomers (DAE-o) convert to the colored closed-ring isomers (DAE-c), while the back reaction is induced only by visible light irradiation. A multiple photoswitching of diarylethenes usually results in irreversible photorearrangement of DAE-c to the so-called annulated isomers DAE-a, that are stable thermally and photochemically. In the present communication, structures of a series of diarylethenes as well as their isomers were optimized on the B3LYP/6-31G(d) level of theory. It was disclosed for the first time, that DAE-a destabilized relatively DAE-c by 1.71–14.00 kcal/mol. These results are important for design of photocontrollable molecules and materials, operated in the oneway (permanent manner).","PeriodicalId":20601,"journal":{"name":"PROCEEDINGS OF UNIVERSITIES APPLIED CHEMISTRY AND BIOTECHNOLOGY","volume":"68 1","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2022-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Energy profile of formal 1,2-dyotropic rearrangement of diarylethenes\",\"authors\":\"E. K. Kouame, A. G. Lvov\",\"doi\":\"10.21285/2227-2925-2022-12-1-153-159\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Diarylethenes with thiophene substituents belong to photoswitchable compounds (photoswitches or photochromes). Upon UV irradiation, their colorless open-ring isomers (DAE-o) convert to the colored closed-ring isomers (DAE-c), while the back reaction is induced only by visible light irradiation. A multiple photoswitching of diarylethenes usually results in irreversible photorearrangement of DAE-c to the so-called annulated isomers DAE-a, that are stable thermally and photochemically. In the present communication, structures of a series of diarylethenes as well as their isomers were optimized on the B3LYP/6-31G(d) level of theory. It was disclosed for the first time, that DAE-a destabilized relatively DAE-c by 1.71–14.00 kcal/mol. These results are important for design of photocontrollable molecules and materials, operated in the oneway (permanent manner).\",\"PeriodicalId\":20601,\"journal\":{\"name\":\"PROCEEDINGS OF UNIVERSITIES APPLIED CHEMISTRY AND BIOTECHNOLOGY\",\"volume\":\"68 1\",\"pages\":\"\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2022-04-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"PROCEEDINGS OF UNIVERSITIES APPLIED CHEMISTRY AND BIOTECHNOLOGY\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.21285/2227-2925-2022-12-1-153-159\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"PROCEEDINGS OF UNIVERSITIES APPLIED CHEMISTRY AND BIOTECHNOLOGY","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.21285/2227-2925-2022-12-1-153-159","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Energy profile of formal 1,2-dyotropic rearrangement of diarylethenes
Diarylethenes with thiophene substituents belong to photoswitchable compounds (photoswitches or photochromes). Upon UV irradiation, their colorless open-ring isomers (DAE-o) convert to the colored closed-ring isomers (DAE-c), while the back reaction is induced only by visible light irradiation. A multiple photoswitching of diarylethenes usually results in irreversible photorearrangement of DAE-c to the so-called annulated isomers DAE-a, that are stable thermally and photochemically. In the present communication, structures of a series of diarylethenes as well as their isomers were optimized on the B3LYP/6-31G(d) level of theory. It was disclosed for the first time, that DAE-a destabilized relatively DAE-c by 1.71–14.00 kcal/mol. These results are important for design of photocontrollable molecules and materials, operated in the oneway (permanent manner).