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Upon irradiation with 365\u2005nm UV light, a <jats:italic>p<\/jats:italic>\u2010methoxy\u2010azobenzene derivative get transformed from all\u2010<jats:italic>trans<\/jats:italic> isomer to nearly all\u2010<jats:italic>cis<\/jats:italic> isomer at the photostationary state. The extent of photomodulation of electronic properties in the NHC ring of the <jats:italic>p<\/jats:italic>\u2010methoxy\u2010azobenzene derivative is determined through the Tolman Electronic Parameter (TEP). Iridium complex, [(IAz\u2010OMe)IrCl(CO)<jats:sub>2<\/jats:sub>] was synthesized and infrared spectra were recorded in dichloromethane solution as film in NaCl crystals and by drop\u2010casting in an ATR crystal. Comparison in averaged carbonyl stretching frequency between all\u2010<jats:italic>trans<\/jats:italic> isomer (<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/chem201905161-math-0001.png\" xlink:title=\"urn:x-wiley:09476539:media:chem201905161:chem201905161-math-0001\"\/>\n<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/chem201905161-math-0002.png\" xlink:title=\"urn:x-wiley:09476539:media:chem201905161:chem201905161-math-0002\"\/>\n) and all\u2010<jats:italic>cis<\/jats:italic> isomer (<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/chem201905161-math-0003.png\" xlink:title=\"urn:x-wiley:09476539:media:chem201905161:chem201905161-math-0003\"\/>\n<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/chem201905161-math-0004.png\" xlink:title=\"urn:x-wiley:09476539:media:chem201905161:chem201905161-math-0004\"\/>\n) indicates a significant decrement of \u0394<jats:sup><jats:italic>tt\u2013cc<\/jats:italic><\/jats:sup><jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/chem201905161-math-0005.png\" xlink:title=\"urn:x-wiley:09476539:media:chem201905161:chem201905161-math-0005\"\/>\n<jats:italic><jats:sub>av<\/jats:sub><\/jats:italic>=2.7\u2005cm<jats:sup>\u22121<\/jats:sup> (film) and 3.8\u2005cm<jats:sup>\u22121<\/jats:sup> (ATR). Therefore, moderate to excellent enhancement of electron density (\u0394<jats:sup><jats:italic>tt\u2013cc<\/jats:italic><\/jats:sup> TEP=2.3\u2005cm<jats:sup>\u22121<\/jats:sup> [film] and 3.2\u2005cm<jats:sup>\u22121<\/jats:sup> [ATR]) at the C\u20102 position of the NHC is achieved through <jats:italic>trans<\/jats:italic>\u2192<jats:italic>cis<\/jats:italic> isomerization of the remotely placed azobenzene units. This fine phototuning of electron\u2010donating ability at the catalytic center would pave the way to control NHC\/NHC\u2010metal catalyzed organic transformations through external stimuli.<\/jats:p>","DOI":"10.1002\/chem.201905161","type":"journal-article","created":{"date-parts":[[2020,1,13]],"date-time":"2020-01-13T13:30:16Z","timestamp":1578922216000},"page":"4214-4219","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":16,"title":["Azobenzene Isomerization\u2010Induced Photomodulation of Electronic Properties of N\u2010Heterocyclic Carbenes"],"prefix":"10.1002","volume":"26","author":[{"given":"Aminul","family":"Islam Sk","sequence":"first","affiliation":[{"name":"Department of Oils, Oleochemicals and Surfactants Technology Institute of Chemical Technology, N. P. 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