Jonathan Long, Pascal Retailleau, Juan Xie, Nicolas Bogliotti
{"title":"Steric Bulk-Dependent Photoresponse of Sulfonamide Azobenzene Ligand in Arene Ruthenium(II) Complexes","authors":"Jonathan Long, Pascal Retailleau, Juan Xie, Nicolas Bogliotti","doi":"10.1002/hlca.202300190","DOIUrl":null,"url":null,"abstract":"<p>A series of sulfonamide azobenzenes bearing alkyl substituents of increasing steric bulk at the position <i>ortho</i> to the N=N bond and their corresponding chloro(hexamethylbenzene)ruthenium(II) complexes were synthesized. The latter bearing mono-substituted ligands exhibited an exocyclic azo bond under the <i>E</i> configuration, and underwent reversible <i>E</i>→<i>Z</i> photoisomerization upon irradiation with visible light, followed by thermal <i>Z</i>→<i>E</i> back isomerization upon resting in the dark at 20 °C. In contrast, the corresponding 2,6-dimethyl substituted azobenzene complex, while also exhibiting an exocyclic azo bond, was isolated as the <i>Z-</i>isomer and underwent uncommon solvent dependent irreversible photodissociation of azobenzene ligand upon visible light irradiation. Valuable insights into the photophysical and structural properties of these complexes were gained by combination of computational and X-ray diffraction studies.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":1.5000,"publicationDate":"2023-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202300190","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Helvetica Chimica Acta","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/hlca.202300190","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
A series of sulfonamide azobenzenes bearing alkyl substituents of increasing steric bulk at the position ortho to the N=N bond and their corresponding chloro(hexamethylbenzene)ruthenium(II) complexes were synthesized. The latter bearing mono-substituted ligands exhibited an exocyclic azo bond under the E configuration, and underwent reversible E→Z photoisomerization upon irradiation with visible light, followed by thermal Z→E back isomerization upon resting in the dark at 20 °C. In contrast, the corresponding 2,6-dimethyl substituted azobenzene complex, while also exhibiting an exocyclic azo bond, was isolated as the Z-isomer and underwent uncommon solvent dependent irreversible photodissociation of azobenzene ligand upon visible light irradiation. Valuable insights into the photophysical and structural properties of these complexes were gained by combination of computational and X-ray diffraction studies.
期刊介绍:
Helvetica Chimica Acta, founded by the Swiss Chemical Society in 1917, is a monthly multidisciplinary journal dedicated to the dissemination of knowledge in all disciplines of chemistry (organic, inorganic, physical, technical, theoretical and analytical chemistry) as well as research at the interface with other sciences, where molecular aspects are key to the findings. Helvetica Chimica Acta is committed to the publication of original, high quality papers at the frontier of scientific research. All contributions will be peer reviewed with the highest possible standards and published within 3 months of receipt, with no restriction on the length of the papers and in full color.