We report the first confirmed fluorescence lifetime measurement for a diazirine. We have obtained time-correlated single-photon counting fluorescence decays for adamantyldiazirine in a variety of solvents, over a wide range of temperatures (77-320 K) and across the diazirine absorption band (330-371 nm). The fluorescence Lifetime of the primary decay component is on the order of 240 ps at ambient temperature and increases at lower temperatures. Arrhenius treatment of the fluorescence lifetime data indicates that the rate-limiting barrier for activated processes in the diazirine excited state is between 2.7 and 2.9 kcal/mol. Adamantyldiazirine's fluorescence lifetime appears to be unaffected by deuteration of the solvent, solvent polarity, or excitation energy, We also report and discuss the steady-state absorption and fluorescence emission spectra of adamantyldiazirine in a variety of solvents, as well as the infrared spectrum (KBr). We interpret the spectra with the help of ab initio (RHF/6-31G* and CIS/6-31G*), density functional (B3LYP/6-31G*), and semiempirical (PM3) calculations. The fluorescence quantum yield of adamantyldiazirine at ambient temperature was calculated to be similar to 0.0012. Analysis of our data in the light of previous research leads us to conclude that little or no intermolecular chemistry is attributable to photoexcited adamantyldiazirine in solution at ambient temperature. Rather, fluorescence competes with one or more intramolecular photochemical processes.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSolubility Enhancement and Fluorescence Quenching of Pyrene by Humic Substances: The Effect of Dissolved Oxygen on Quenching ProcessesKarlin M. Danielsen, Yu-Ping. Chin, Jeffrey S. Buterbaugh, Terry L. Gustafson, and Samuel J. TrainaCite this: Environ. Sci. Technol. 1995, 29, 8, 2162–2165Publication Date (Print):August 1, 1995Publication History Published online1 May 2002Published inissue 1 August 1995https://pubs.acs.org/doi/10.1021/es00008a042https://doi.org/10.1021/es00008a042research-articleACS PublicationsRequest reuse permissionsArticle Views473Altmetric-Citations67LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts