Tetrazolo[1,5-a]quinazoline (9) is converted to 2-azidoquinazoline (10) on sublimation at 200 degrees C and above, and the azide-tetrazole equilibrium is governed by entropy. 2-Quinazolylnitrenes 11 and 27 and/or their ring expansion products 14 and 29 can undergo type I (ylidic) and type II (diradicaloid) ring opening. Argon matrix photolysis of 9/10 affords 2-quinazolylnitrene (11), which has been characterized by ESR, UV, and IR spectroscopy. A minor amount of a second nitrene, formed by rearrangement or ring opening, is also observed. A diradical (19) is formed rapidly by type II ring opening and characterized by ESR spectroscopy; it decays thermally at 15 K with a half-life of ca. 47 min, in agreement with its calculated facile intersystem crossing (19T --> 19OSS) followed by facile cyclization/rearrangement to 1-cyanoindazole (21) (calculated activation barrier 1-2 kcal/mol) and N-cyanoanthranilonitrile (22). 21and 22 are the isolated end products of photolysis. 21 is also the end product of flash vacuum thermolysis. An excellent linear correlation between the zero-field splitting parameter D (cm(-1)) and the spin density rho on the nitrene N calculated at the B3LYP/EPRIII level is reported (R2 = 0.993 for over 100 nitrenes). Matrix photolysis of 3-phenyltetrazolo[1,5-a]quinazoline (25) affords the benzotriazacycloheptatetraene 29, which can be photochemically interconverted with the type I ring opening product 2-isocyano-alpha-diazo-alpha-phenyltoluene (33) as determined by IR and UV spectroscopy. The corresponding carbene 37, obtained by photolysis of 33, was detected by matrix ESR spectroscopy.
Novel enzyme activity: Biocatalytic Henry reactions with nitromethane and nitroethane yielded the corresponding nitroalcohols with good enantio‐ and diastereocontrol in the presence of the hydroxynitrile lyase from the tropical rubber tree Hevea brasiliensis. Molecular modeling and deuterated starting materials were used in mechanistic investigations.
The emissive output of indicator dyes in luminescent sensors can be amplified by the addition of antenna dyes with a higher brightness. The highly concentrated antenna dye molecules absorb the excitation light and transfer the energy to an indicator dye. This harvesting of light makes thin sensor layers (thickness <500 nm) and nanometer sized sensor particles with exceptionally high brightness and compatible with the most powerful LEDs available. The performance of sensor layers of ∼250 nm thickness employing light harvesting was investigated and compared with established sensors. The principle is demonstrated for oxygen and ammonia sensors. An overview of possible application of light harvesting to various reagent mediated optical sensing schemes is given.
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