Generation of boryl-nitroxide radicals from a boraalkene via the nitroso ene reaction.

Examples of isolated boron substituted nitroxide radicals are rare. The reaction of the reactive cyclic boraalkene 3 with nitrosobenzene yields a mixture of the [2 + 2] cycloaddition product 4a, the B-nitroxide radicals 5a and 6a and the azoxybenzene co-product 7avia a bora nitroso ene reaction pathway, the boron analogue of the nitroso ene reaction. The products were separated by flash chromatography, and the B-nitroxide radicals were characterized by X-ray diffraction and EPR spectroscopy. Radical 5a was shown to be a hydrogen atom abstractor. Both the B-nitroxide radicals are more easily oxidized compared to e.g. TEMPO, as shown by cyclic voltammetry.

Oxy-Borylenes as Photoreductants: Synthesis and Application in Dehalogenation and Detosylation Reactions.

While the range of accessible borylenes has significantly broadened over the last decade, applications remain limited. Herein, we present tricoordinate oxy-borylenes as potent photoreductants that can be readily activated by visible light. Facile oxidation of CAAC stabilized oxy-borylenes (CAAC)(IPr2 Me2 )BOR (R=TMS, CH2 CH2 C6 H5 , CH2 CH2 (4-F)C6 H4 ) to their corresponding radical cations is achieved with mildly oxidizing ferrocenium ion. Cyclovoltammetric studies reveal ground-state redox potentials of up to -1.90 V vs. Fc+/0 for such oxy-borylenes placing them among the strongest organic super electron donors. Their ability as photoreductants is further supported by theoretical studies and showcased by the application as stoichiometric reagents for the photochemical hydrodehalogenation of aryl chlorides, aryl bromides and unactivated alkyl bromides as well as the detosylation of anilines.

Photoresponsive host-guest chemistry and relaxation time of fluorinated cyclodextrin and arylazopyrazole-functionalized DOTA metal complexes.

Light-responsive modulation of the longitudinal (T1) and transversal relaxation times of a fluorinated cyclodextrin has been achieved by host-guest complexation with arylazopyrazole-modified metal complexes in aqueous solution. This supramolecular concept can potentially be applied to the development of contrast agents for 19F magnetic resonance imaging (MRI).

Electronic effects in profluorescent benzotriazinyl radicals: a combined experimental and theoretical study.

The synthesis, photophysical characterization, and quantum chemical calculations of a series of benzotriazinyl radicals and their styryl radical trapping products are presented. The benzotriazinyl radicals are non-luminescent but surprisingly the corresponding styryl radical trapping products exhibit high fluorescence quantum yields (up to 60% in some cases), making them highly valuable probes or labels. Additionally, the influence of the substitution pattern on the optical properties of the radical trapping products was observed experimentally and interpreted by means of quantum chemical calculations. Specific substitution patterns showed a bathochromic shift compared to the unsubstituted compound. Computationally, it was shown that this substitution pattern leads to a stronger energetic stabilization of the lowest unoccupied molecular orbital than the highest occupied molecular orbital. Analysis of the influence of the substitution pattern on the optical properties showed a bathochromic shift in several examples, which was interpreted by means of quantum chemical calculations.

Bis-Anthracene Fused Porphyrin as an Efficient Photocatalyst: Facile Synthesis and Visible-Light-Driven Oxidative Coupling of Amines.

Development of high-performance photocatalysts for the conversion of amines is of great importance, but has remained a challenging task. Here, a bis-anthracene fused porphyrin (AFP) was synthesized in a high yield by a facile synthetic protocol, which involves a Suzuki coupling for the conjugation of two anthracene groups with a porphyrin ring, followed by oxidative cyclodehydrogenation. When serving as a photocatalyst, AFP exhibits an outstanding photocatalytic performance for the visible-light-induced aerobic oxidation of amines to imines at ambient conditions. Density functional theory calculations revealed that the low energy band gap, caused by the large planar and π-extended porphyrin structure of AFP, contributed to its high photocatalytic performance.

Effect of the C(3)-Substituent in Verdazyl Radicals on their Profluorescent Behavior.

Methods for the detection of reactive intermediates such as transient radicals are important in organic chemistry, polymer chemistry, biology or medicine. Along these lines we recently reported that 1,5-diphenyl-6-oxo verdazyl radicals can be used as fluorescent spin sensors. In situ generated C-centered radicals are efficiently trapped by the verdazyls, which in turn undergo transformation from a paramagnetic non-fluorescent state to a diamagnetic fluorescent state. Whereas the N-phenyl substituent in the spin probes is of high importance for obtaining profluorescent behavior, the effect of the C(3)-substituent has not been investigated to date. We herein present the synthesis and characterization of various 1,5-diphenyl-6-oxo-verdazyl radicals bearing differently hybridized C-substituents at the C(3) position. Steady-state and time-resolved fluorescence spectroscopy in solution and in the solid state along with time-dependent density functional theory (TDDFT) calculations reveal that a C(3)-aryl substituent is crucial for obtaining fluorescence after spin trapping. In addition, it is shown that the emission wavelength of the C(3)-aryl substituted verdazyl derivatives can be tuned by selective destabilization of the HOMO and the LUMO.