Photoelimination of nitrogen from adamantine and pentacycloundecane (PCU) diazirines: a spectroscopic study and supramolecular control

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dc.contributor.authorŠumanovac, Tatjana
dc.contributor.authorAlešković, Marija
dc.contributor.authorŠekutor, Marina
dc.contributor.authorMatković, Marija
dc.contributor.authorBaron, Thibaut
dc.contributor.authorMlinarić-Majersk, Kata
dc.contributor.authorBohne, Cornelia
dc.contributor.authorBasarić, Nikola
dc.date.accessioned2020-07-16T21:42:47Z
dc.date.available2020-07-16T21:42:47Z
dc.date.copyright2019en_US
dc.date.issued2019
dc.description.abstractPhotochemical reactivity of pentacycloundecane (PCU) and adamantane diazirines was investigated by preparative irradiation in different solvents, laser flash photolysis (LFP) and quantum chemical computations. In addition, formation of inclusion complexes for diazirines with cucurbit[7]uril, β- and γ-cyclodextrin (β- and γ-CD) was investigated by 1H NMR spectroscopy, isothermal microcalorimetry and circular dichroism spectroscopy, followed by the investigation of photochemical reactivity of the formed complexes. Diazirines undergo efficient photochemical elimination of nitrogen (ΦR > 0.5) and deliver the corresponding singlet carbenes. Singlet carbenes react in intra- and intermolecular reactions and we found a rare singlet carbene pathway in CH3OH involving protonation and formation of a carbocation, detected due to the specific rearrangement of the pentacycloundecane skeleton. Singlet diazirines undergo intersystem crossing and deliver triplet carbenes that react with oxygen to form ketones which were isolated after irradiation. Our main finding is that the formation of diazirine inclusion complexes with β-CD and γ-CD changes the relative ratio of singlet vs. triplet pathways, with singlet carbene products being dominant from the chemistry of the irradiated complexes. Our combined theoretical and experimental studies provide new insights into the supramolecular control of carbene reactivity which has possible applications for the control of product distribution by solvent effects and the choice of constrained media.en_US
dc.description.reviewstatusRevieweden_US
dc.description.scholarlevelFacultyen_US
dc.description.sponsorshipThese materials are based on work financed by the Croatian Science Foundation (HRZZ IP-2014-09-6312), the Natural Sciences and Engineering Research Council of Canada (CB, NSERC-RGPIN-121389-2012), and the University of Victoria (UVic). CB thanks CAMTEC for the use of shared facilities. NB thanks Professor P. Wan and the University of Victoria, Canada, BC for the financial support during the visit to UVic. MŠ thanks Professor Peter R. Schreiner for kindly providing computational resources of the Justus-Liebig-University, Giessen, Germany.en_US
dc.identifier.citationŠumanovac, T., Alešković, M., Šekutor, M., Matković, M., Baron, T., Mlinarić-Majerski, K., Bohne, C., & Basarić, N. (2019). Photoelimination of nitrogen from adamantine and pentacycloundecane (PCU) diazirines: a spectroscopic study and supramolecular control. Photochemical & Photobiological Sciences, 7, 1806-1822. https://doi.org/10.1039/C9PP00124G.en_US
dc.identifier.urihttps://doi.org/10.1039/C9PP00124G
dc.identifier.urihttp://hdl.handle.net/1828/11936
dc.language.isoenen_US
dc.publisherRoyal Society of Chemistryen_US
dc.titlePhotoelimination of nitrogen from adamantine and pentacycloundecane (PCU) diazirines: a spectroscopic study and supramolecular controlen_US
dc.typePostprinten_US

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