Thiophenylazobenzene: An Alternative Photoisomerization Controlled by Lone-Pair⋅⋅⋅π Interaction

Azoheteroarene photoswitches have attracted attention due to their unique properties. We present the stationary photochromism and ultrafast photoisomerization mechanism of thiophenylazobenzene (TphAB). It demonstrates impressive fatigue resistance and photoisomerization efficiency, and shows favorably separated (E)- and (Z)-isomer absorption bands, allowing for highly selective photoconversion. The (Z)-isomer of TphAB adopts an unusual orthogonal geometry where the thiophenyl group is perfectly perpendicular to the phenyl group. This geometry is stabilized by a rare lone-pair⋅⋅⋅π interaction between the S atom and the phenyl group. The photoisomerization of TphAB occurs on the sub-ps to ps timescale and is governed by this interaction. Therefore, the adoption and disruption of the orthogonal geometry requires significant movement along the inversion reaction coordinates (CNN and NNC angles). Our results establish TphAB as an excellent photoswitch with versatile properties that expand the application possibilities of AB derivatives.     

Effects of the photocathode non-uniformity on radon measurements by plastic scintillation spectrometry

Journal of Radioanalytical and Nuclear Chemistry - This work shows a study of the effect of the non-uniformity of photocathode response on the energy resolution of plastic scintillators optimized...     

Thiophenylazobenzene: An Alternative Photoisomerization Controlled by Lone‐Pair⋅⋅⋅π Interaction

Azoheteroarene photoswitches have attracted attention due to their unique properties. We present the stationary photochromism and ultrafast photoisomerization mechanism of thiophenylazobenzene (TphAB). It demonstrates impressive fatigue resistance and photoisomerization efficiency, and shows favorably separated (E)‐ and (Z)‐isomer absorption bands, allowing for highly selective photoconversion. The (Z)‐isomer of TphAB adopts an unusual orthogonal geometry where the thiophenyl group is perfectly perpendicular to the phenyl group. This geometry is stabilized by a rare lone‐pair???π interaction between the S atom and the phenyl group. The photoisomerization of TphAB occurs on the sub‐ps to ps timescale and is governed by this interaction. Therefore, the adoption and disruption of the orthogonal geometry requires significant movement along the inversion reaction coordinates (CNN and NNC angles). Our results establish TphAB as an excellent photoswitch with versatile properties that expand the application possibilities of AB derivatives.     

Photoresponsive Formation of an Intermolecular Minimal G‐Quadruplex Motif

The ability of three different bifunctional azobenzene linkers to enable the photoreversible formation of a defined intermolecular two‐tetrad G‐quadruplex upon UV/Vis irradiation was investigated. Circular dichroism and NMR spectroscopic data showed the formation of G‐quadruplexes with K⁺ ions at room temperature in all three cases with the corresponding azobenzene linker in an E conformation. However, only the para–para‐substituted azobenzene derivative enables photoswitching between a nonpolymorphic, stacked, tetramolecular G‐quadruplex and an unstructured state after E–Z isomerization.     

Synthesis and characterisation of scintillating microspheres made of polystyrene/polycarbonate for <Superscript>222</Superscript>Rn measurements

Several studies have demonstrated that polycarbonate-based polymers have good capacities for the absorption of ²²²Rn. Meanwhile, polystyrene polymers are reported to be the most appropriate for developing plastic scintillator materials for the detection of radioactivity. The objective of this work was to develop plastic scintillators in the form of microspheres (PSm) composed of polystyrene and polycarbonate that could be used to measure ²²²Rn and improve this performance thanks to the combination of characteristics of both polymers. Our results show that PSm of polystyrene and polycarbonate can be made via the evaporation/extraction method, despite the two polymers not being miscible. From the point of view of the radioactive measurements, we observed that the addition of polycarbonate causes quenching, although it does not significantly affect the detection efficiency for alpha and high-energy beta emitters. From the point of view of ²²²Rn absorption, we observed that synthesis of the PSm through the evaporation/extraction method changes the ²²²Rn absorption of the raw material. This result demonstrates that the method of production of the polymer and the resulting physical characteristics are a key parameter for its final ²²²Rn absorption properties.     

Molybdenum HDS catalysts supported on niobia-silica

The effect of the amount of Nb₂O₅on the dispersion and reductive properties of Mo/Nb₂O₅-SiO₂ catalysts has been studied. Addition of niobium leads to an increase of the dispersion, and the reducibility of molybdenum. A synergetic effect of niobium on the catalytic activity in hydrodesulfurization of thiophene was observed at 5.4 wt.% of Nb₂O₅. This revised version was published online in June 2006 with corrections to the Cover Date.     

Excited State Processes in 1-Deazariboflavin Studied by Ultrafast Fluorescence Kinetics

The photochemical reactions of the 1-deaza derivative of riboflavin (RF) have been studied by sub-ps time-resolved fluorescence spectroscopy. A potential effect of the solvent polarity and hydrogen bonding capability on the excited state (ES) dynamics was tested by measuring 1-deaza RF in water and, after acetylation of the sugar moiety, also in acetonitrile. Opposite to former reports, which indicated no fluorescence after laser excitation (Spencer et al. [1977] Biochemistry 16 : 3586–3594), we find a significant fluorescence in either solvent. For both compounds, the fluorescence decays are biexponential with lifetimes in the ps time domain (1.8 and 12.5 ps for 1-deaza RF, and 3 and 87 ps for Ac₄-1-deaza RF). In addition, a third, independent fluorescence decay was observed for both compounds. The remarkably slower second decay process for the measurements of the tetra-acetyl derivative in acetonitrile points to the involvement of hydrogen bonding or changes in the protonation/tautomerization state in the ES. In contrast to the parent compound (RF), no triplet state formation can be detected for 1-deaza RF, making the internal conversion and the fluorescence the only decay processes of the ES.     

Polysubstituted 5‐Phenylazopyrimidines: Extremely Fast Non‐ionic Photochromic Oscillators

Photochromic systems with an ultrahigh rate of thermal relaxation are highly desirable for the development of new efficient photochromic oscillators. Based on DFT calculations, we designed a series of 5‐phenylazopyrimidines with strong push–pull character in silico and observed very low energy barriers for the thermal (Z)‐to‐(E) isomerization. The structure of the (Z)‐isomer of the slowest isomerizing derivative in the series was confirmed by NMR analysis with in situ irradiation at low temperature. The substituents can tune the lifetime of thermal back isomerization from hundreds of microseconds to several nanoseconds (8 orders of magnitude). The photoswitching parameters were extracted from transient absorption techniques and a dominant rotation mechanism of the (Z)‐to‐(E) thermal fading was proposed based on DFT calculations.     

Polysubstituted 5-Phenylazopyrimidines: Extremely Fast Non-ionic Photochromic Oscillators

Photochromic systems with an ultrahigh rate of thermal relaxation are highly desirable for the development of new efficient photochromic oscillators. Based on DFT calculations, we designed a series of 5-phenylazopyrimidines with strong push–pull character in silico and observed very low energy barriers for the thermal (Z)-to-(E) isomerization. The structure of the (Z)-isomer of the slowest isomerizing derivative in the series was confirmed by NMR analysis with in situ irradiation at low temperature. The substituents can tune the lifetime of thermal back isomerization from hundreds of microseconds to several nanoseconds (8 orders of magnitude). The photoswitching parameters were extracted from transient absorption techniques and a dominant rotation mechanism of the (Z)-to-(E) thermal fading was proposed based on DFT calculations.