Dataset Information

Profluorescent verdazyl radicals - synthesis and characterization.

ABSTRACT: The synthesis and characterization of various 6-oxo-verdazyl radicals and their diamagnetic styryl radical trapping products are presented. It is shown that styryl radical trapping products derived from N-phenyl verdazyls show fluorescence whereas the N-methyl congeners are non-fluorescent. In the parent N-phenyl verdazyls fluorescence is fully quenched which renders these compounds highly valuable profluorescent radical probes.

SUBMITTER: Matuschek D

PROVIDER: S-EPMC5667500 | biostudies-other | 2015 Aug

REPOSITORIES: biostudies-other

ACCESS DATA

Publications

Profluorescent verdazyl radicals - synthesis and characterization.

Matuschek David D Eusterwiemann Steffen S Stegemann Linda L Doerenkamp Carsten C Wibbeling Birgit B Daniliuc Constantin G CG Doltsinis Nikos L NL Strassert Cristian A CA Eckert Hellmut H Studer Armido A

Chemical science 20150605 8

The synthesis and characterization of various 6-oxo-verdazyl radicals and their diamagnetic styryl radical trapping products are presented. It is shown that styryl radical trapping products derived from N-phenyl verdazyls show fluorescence whereas the N-methyl congeners are non-fluorescent. In the parent N-phenyl verdazyls fluorescence is fully quenched which renders these compounds highly valuable profluorescent radical probes. ...[more]

PMID: 29142709

Similar Datasets

Project description:Heterogeneous phase astrochemistry plays an important role in the synthesis of complex organic matter (COM) as found on comets and rocky body surfaces like asteroids, planetoids, moons and planets. The proposed catalytic model is based on two assumptions: (a) siliceous rocks in both crystalline or amorphous states show surface-exposed defective centers such as siloxyl (Si-O•) radicals; (b) the second phase is represented by gas phase CO molecules, an abundant C1 building block found in space. By means of quantum chemistry; (DFT, PW6B95/def2-TZVPP); the surface of a siliceous rock in presence of CO is modeled by a simple POSS (polyhedral silsesquioxane) where a siloxyl (Si-O•) radical is present. Four CO molecules have been consecutively added to the Si-O• radical and to the nascent polymeric CO (pCO) chain. The first CO insertion shows no activation free energy with ΔG200K = -21.7 kcal/mol forming the SiO-CO• radical. The second and third CO insertions show Δ G200K‡ ≤ 10.5 kcal/mol. Ring closure of the SiO-CO-CO• (oxalic anhydride) moiety as well as of the SiO-CO-CO-CO• system (di-cheto form of oxetane) are thermodynamically disfavored. The last CO insertion shows no free energy of activation resulting in the stable five member pCO ring, precursor to 1,4-epoxy-1,2,3-butanone. Hydrogenation reactions of the pCO have been considered on the SiO oxygen or on the carbons and oxygens of the pCO chains. The formation of the reactive aldehyde SiO-CHO on the siliceous surface is possible. In principle, the complete hydrogenation of the (CO)1-4 series results in the formation of methanol and polyols. Furthermore, all the SiO-pCO intermediates and the lactone 1,4-epoxy-1,2,3-butanone product in its radical form can be important building blocks in further polymerization reactions and/or open ring reactions with H (aldehydes, polyols) or CN (chetonitriles), resulting in highly reactive multi-functional compounds contributing to COM synthesis.

Dataset Information

Profluorescent verdazyl radicals - synthesis and characterization.

Publications

Profluorescent verdazyl radicals - synthesis and characterization.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets