Synthesis and spectroscopic analysis of tetraphenylporphyrinatoantimony(V) complexes linked to boron-dipyrrin chromophore on axial ligands

Tetraphenylporphyrinatoantimony(V) complexes, linked to boron-dipyrrin chromophores on axial ligands, were synthesized. The fluorescence spectra of 1a, 1b and 1c (3-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]propoxo(methoxo)antimony(V) tetraphenylporphyrin bromide (1a); 6-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]hexyloxo(methoxo)antimony(V) tetraphenylporphyrin bromide (1b); bis{3-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]propoxo}antimony(V) tetraphenylporphyrin bromide (1c)) were analyzed under the excitations of N,N′-difluorobornyl-5-dipyrrinylphenyl (Bdpy) and tetraphenylporphyrinatoantimony(V) (Sb(TPP)) chromophores. Under the irradiation of Bdpy chromophore, the excitation energy was transferred from Bdpy chromophore to the Sb(TPP) moiety at 0.13–0.40 of the quantum yields, even in a polar solvent. On the other hand, the emission of Sb(TPP) chromophores was quenched by Bdpy chromophores at rate constants of 10⁸–10⁹ s⁻¹, independent of on the solvent polarity. Under the excitation of the Bdpy chromophore of 1d (3-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]propoxo(phenyloxo)antimony(V) tetraphenylporphyrin bromide) involving both the Bdpy and the phenoxy chromophores on the axial ligands, the excited singlet state of the Sb(TPP) chromophore generated by the energy transfer from the Bdpy chromophore was quenched by the phenoxy ligand via non-radiative processes involving electron transfer. However, rapid back electron-transfer may occur because no absorption of the anion radical of Sb(TPP) was observed by nanosecond laser photolysis.     

Zirconium-mediated intramolecular ester transfer reaction: synthesis of alpha-substituted gamma-aminobutyric acid (GABA) derivatives

[reaction: see text]. The zirconium-mediated intramolecular ester transfer reaction of N-alkenyl carbamate derivatives proceeded to give alpha-substituted gamma-aminobutyric acid (GABA) derivatives in good to excellent yields. Quenching experiments of the reaction mixture with iodine or O2 indicated the presence of a cyclopropane intermediate. The resulting iodide was converted to 2-substituted pyrrolidine-3-carboxylate and/or alpha-alkylidene-gamma-aminobutyric acid derivatives in a stereospecific manner.     

Furopyridines. XXIII. Synthesis and reactions of chloropyridine derivatives of furo[2,3-b]-, -[2,3-c]- and -[3,2-c]pyridine

Chlorination of the N-oxides of furo[2,3-b]- 1a , -[2,3-c]- 1b and -[3,2-c]pyridine 1c with phosphorus oxychloride afforded compounds substituted normally at the α- or λ-position to the ring nitrogen, 2a, 2′a, 2b, 2c, 2′c and 2′c , and in addition, in the case of 1b , compounds substituted on the furan ring, 2′b and 2″b . The structures of these compounds were confirmed from their ir, nmr and mass spectra. The major chlorinated products 2a, 2b and 2c were converted to methoxy- 5a, 5b and 5c , N-pyrrolidyl- 7a, 7b and 7c , and phenylthiofuropyridines 8a, 8b , and 8c .     

Highly Efficient α‐Sialylation by Virtue of Fixed Dipole Effects of N‐Phthalyl Group: Application to Continuous Flow Synthesis of α(2‐3)‐and α(2‐6)‐Neu5Ac‐Gal Motifs by Microreactor

Highly α‐selective sialylation of sialic acid N‐phenyltrifluoroacetimidate with various galactose and lactose acceptors has been achieved by introducing the C‐5 N‐phthalyl group on the donor. The “fixed dipole effect” of the N‐phthalyl group was proposed to explain the high reactivity and α‐selectivity. The microfluidic system was applied to the present α‐sialylation, which is amenable to large‐scale synthesis. The N‐phthalyl group was removed by treatment with methylhydrazine acetate, for which protocol can be readily applied to the synthesis of a variety of sialic acid‐containing oligosaccharides.      

Chiral Iodotriptycenes: Synthesis and Catalytic Applications

Invited for this month′s cover picture is the group of Thomas Wirth at Cardiff University (UK). The cover picture shows two structures of triptycenes. In each of these molecules all three aromatic rings are different with the rigid structure of the molecules making them chiral. The two sp³-carbons shown in red and green are the stereocentres with defined configuration. These molecules contain the crucial iodine functionality which are utilised to generate hypervalent iodine(III)-catalysts in situ . The authors acknowledge Dr. Yu Wang for the creation of the cover image. Read the full text of their Research Article at 10.1002/open.202200145 .     

Selective ablation of atherosclerotic lesions with less thermal damage by controlling the pulse structure of a quantum cascade laser in the 5.7-µm wavelength range

Cholesteryl esters are the main components of atherosclerotic plaques, and they have an absorption peak at the wavelength of 5.75 µm. To realize less-invasive ablation of the atherosclerotic plaques using a quasi-continuous wave (quasi-CW) quantum cascade laser (QCL), the thermal effects on normal vessels must be reduced. In this study, we attempted to reduce the thermal effects by controlling the pulse structure. The irradiation effects on rabbit atherosclerotic aortas using macro pulse irradiation (irradiation of pulses at intervals) and conventional quasi-CW irradiation were compared. The macro pulse width and the macro pulse interval were determined based on the thermal relaxation time of atherosclerotic and normal aortas in the oscillation wavelength of the QCL. The ablation depth increased and the coagulation width decreased using macro pulse irradiation. Moreover, difference in ablation depth between the atherosclerotic and normal rabbit aortas using macro pulse irradiation was confirmed. Therefore, the QCL in the 5.7-µm wavelength range with controlling the pulse structure was effective for less-invasive laser angioplasty.     

Determination of the scattering coefficient of biological tissue considering the wavelength and absorption dependence of the anisotropy factor

The anisotropy factor g, one of the optical properties of biological tissues, has a strong influence on the calculation of the scattering coefficient μ _s in inverse Monte Carlo (iMC) simulations. It has been reported that g has the wavelength and absorption dependence; however, few attempts have been made to calculate μ _s using g values by taking the wavelength and absorption dependence into account. In this study, the angular distributions of scattered light for biological tissue phantoms containing hemoglobin as a light absorber were measured by a goniometric optical setup at strongly (405 nm) and weakly (664 nm) absorbing wavelengths to obtain g. Subsequently, the optical properties were calculated with the measured values of g by integrating sphere measurements and an iMC simulation, and compared with the results obtained with a conventional g value of 0.9. The μ _s values with measured g were overestimated at the strongly absorbing wavelength, but underestimated at the weakly absorbing wavelength if 0.9 was used in the iMC simulation.     

Perfectly conducting channel and universality crossover in disordered graphene nanoribbons

The band structure of graphene ribbons with zigzag edges have two valleys well separated in momentum space, related to the two Dirac points of the graphene spectrum. The propagating modes in each valley contain a single chiral mode originating from a partially flat band at the band center. This feature gives rise to a perfectly conducting channel in the disordered system, if the impurity scattering does not connect the two valleys, i.e., for long-range impurity potentials. Ribbons with short-range impurity potentials, however, through intervalley scattering display ordinary localization behavior. The two regimes belong to different universality classes: unitary for long-range impurities and orthogonal for short-range impurities.     

High Diastereoselection of a Dissymmetric Capsule by Chiral Guest Complexation

Encapsulation of chiral guests in the dissymmetric capsule 1?4 BF₄ formed diastereomeric supramolecular complexes G ? 1?4 BF₄ ( G : guest). When chiral guests 2 a – q were encapsulated within the dissymmetric space of the self‐assembled capsule 1?4 BF₄, circular dichroism (CD) was observed at the absorption bands that are characteristic of the π–π* transition of the bipyridine moiety of the capsule, which suggests that the P and M helicities of the capsule are biased by the chiral guest complexation. The P helicity of diastereomeric complex (S)‐ 2 l ? 1?4 BF₄ was determined to be predominant, based on CD exciton coupling theory and DFT calculations. The diastereoselectivity was highly influenced by the ester substituents, such that benzyl ester moieties were good for improving the diastereoselectivity. A diastereomeric excess of 98 % was achieved upon the complexation of 2 j . The relative enthalpic and entropic components for the distereoselectivity were obtained from a van’t Hoff plot. The enthalpic components were linearly correlated with the substituent Hammett parameters (σ_p⁺). The electron‐rich benzyl ester moieties generated donor–acceptor π–π stacking interactions with the bipyridine moiety, which resulted in a significant difference in energy between the predominant and subordinate diastereomeric complexes.     

Mechanochromic Delayed Fluorescence Switching in Propeller‐Shaped Carbazole–Isophthalonitrile Luminogens with Stimuli‐Responsive Intramolecular Charge‐Transfer Excited States

Herein, the universal design of high‐efficiency stimuli‐responsive luminous materials endowed with mechanochromic luminescence (MCL) and thermally activated delayed fluorescence (TADF) functions is reported. The origin of the unique stimuli‐triggered TADF switching for a series of carbazole–isophthalonitrile‐based donor–acceptor (D–A) luminogens is demonstrated based on systematic photophysical and X‐ray analysis, coupled with theoretical calculations. It was revealed that a tiny alteration of the intramolecular D–A twisting in the excited‐state structures governed by the solid morphologies is responsible for this dynamic TADF switching behavior. This concept is applicable to the fabrication of bicolor emissive organic light‐emitting diodes using a single TADF emitter.