Photolysis of adamantane-2-spiru-3?-diazirine

Isaev, S. D.; Sherstyuk, V. P.; Kozlov, U. F.; Skripkin, V. V.; Yanku, I.

doi:10.1007/bf01372474

Cited by 4 publications

(14 citation statements)

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“…g ., adamantylidene or 2-diazoadamantane), and not that of the diazirine excited state. The lack of a solvent dependence or noticeable oxygen dependence for the fluorescence lifetime also seems to be inconsistent with the hypothesis that exciplexes of certain solvents or triplet oxygen ( 3 O 2 ) with the excited state of adamantyldiazirine might be responsible for some of the observed photochemistry …”

Section: Discussionmentioning

confidence: 76%

“…When the sample was subjected to extensive 350-nm photolysis, the contribution of the long-lived component reached 69%, even when monitored at 390 nm. Among the photoproducts that have been observed previously, ,,, adamantanone and adamantanone azine possess chromophores that would make them possible sources of the long-lived fluorescence. It is possible, however, that the species responsible for the fluorescence is formed in microscopic quantities and has gone undetected in previous analyses, owing to the extreme sensitivity of fluorescence techniques relative to other methods such as gas chromatography.…”

Section: Discussionmentioning

confidence: 98%

“…Adamantyldiazirine has attracted the attention of several investigators. ,− This is due, in part, to the fact that adamantyldiazirine is easy to synthesize, and is a stable, crystalline solid that is easy to handle. The carbene anticipated from the fragmentation of the diazirine must surmount substantial barriers to intramolecular rearrangement of carbon or hydrogen, owing to the highly strained nature of the products of such reactions.…”

Section: Introductionmentioning

confidence: 99%

“…They have measured the quantum yields of formation for the transient species 2-diazoadamantane ( φ diazo ∼ 0.5) and adamantylidene ( φ carbene ∼ 0.5) in isooctane solutions. Previous studies had only analyzed the stable photoproducts. − , These stable photoproducts vary with solvent. Some of the most commonly observed are adamantanone, adamantanone azine, 2,4-dehydroadamantane, and solvent insertion products.…”

Section: Introductionmentioning

confidence: 99%

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Fluorescence Lifetime Measurements and Spectral Analysis of Adamantyldiazirine

et al. 1997

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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 ∼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.

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Section: Discussionmentioning

confidence: 76%

Section: Discussionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Fluorescence Lifetime Measurements and Spectral Analysis of Adamantyldiazirine

et al. 1997

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“…If conversion of diazirine 1 was not complete, the amount of 2,4-dehydroadamantane (4) could not be determined by GC because of decomposition of 1 to 2,4-dehydroadamantane (4) in the injector. Here, 13C NMR spectroscopy was used to determine the product ratios of 2,4-dehydroadamantane (4), adaman tanone (5), and 2-adamantanol (6). Signal intensities of the product mixture obtained were compared to those of a standard solution of 2,4-dehydroadamantane (4), adaman tanone (5), and 2-adamantanol (6).…”

Section: Methodsmentioning

confidence: 99%

Carbene rearrangements. 43. Carbenes in Constrained Systems. 2. First Carbene Reactions within Zeolites: Solid-State Photolysis of Adamantane-2-spiro-3'-diazirine

Kupfer¹,

Poliks²,

Brinker³

1994

J. Am. Chem. Soc.

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Inclusion complexes of adamantane2-spiro-3'-diazirine (1) in different X-and Y-type zeolites (faujasite) have been prepared. These complexes were analyzed by FT-IR and '3C CP-MAS NMR spectroscopy. The guest-host complexes were irradiated with UV light in the solid state and the reaction products separated from the host and analyzed. Product ratios obtained in zeolites are totally different from those obtained by irradiation of 1 in solution or as a pure compound. In zeolites the main products isolated are 2A-dehydroadamantane (4) and 2-adamantanol (6). In addition, adamantanone (5) and adamantane are formed. While 2-adamantanol(6) is thought to be a product from an acid-catalyzed reaction, the strained 2,4-dehydroadamantane (4) derives from an intramolecular 1,3 C-H insertion of adamantanylidene (3). In stark contrast to reactions in solution, in zeolites the formation of adamantanone azine (7) resulting from an intermolecular reaction is only of minor significance.

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Cucurbituril Adamantanediazirine Complexes and Consequential Carbene Chemistry

et al. 2012

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Adamantanediazirines, precursors of adamantanylidenes, form 1:1 complexes (guest to host) with cucurbit[7]uril and cucurbit[8]uril and a 3:1 complex with a Pd nanocage in water. (1)H NMR spectra suggested that these complexes are stable in water on the NMR time scale. While photolysis of adamantanediazirines in water gave mainly adamantanone and adamantanol via adamantanylidene as intermediate, the 1:1 complexes of adamantanediazirine with cucurbiturils gave intramolecular C-H insertion products of adamantanylidene in >90% yield. The study establishes that significant control of carbene reactivity can be achieved when the precursor is encapsulated within a tight inert cavity. While the general characteristics of molecular containers can be understood on the basis of concepts such as "confinement" and "weak interactions", each one is unique and deserves careful scrutiny.

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Photolysis of adamantane-2-spiru-3?-diazirine

Cited by 4 publications

References 10 publications

Fluorescence Lifetime Measurements and Spectral Analysis of Adamantyldiazirine

Fluorescence Lifetime Measurements and Spectral Analysis of Adamantyldiazirine

Carbene rearrangements. 43. Carbenes in Constrained Systems. 2. First Carbene Reactions within Zeolites: Solid-State Photolysis of Adamantane-2-spiro-3'-diazirine

Cucurbituril Adamantanediazirine Complexes and Consequential Carbene Chemistry

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