Visible‐Light‐Mediated Addition of α‐Aminoalkyl Radicals to [60]Fullerene by Using Photoredox Catalysts

The functionalization of fullerene has been extensively studied and various fullerene derivatives have been synthesized. We have succeeded in the functionalization of [60]fullerene by using α‐aminoalkyl radicals generated by visible‐light‐mediated single‐electron oxidation of α‐silylamines as synthetic intermediates. In these reactions, the introduction of diarylamino groups, which are useful electron donors, has been easily achieved.     

Thermodynamic study on the interaction of imidazolium salts and POE-type nonionic surfactant in the adsorbed film

The composition of the adsorbed film and the excess Gibbs energy of adsorption $ {\widehat{g}}^{\mathrm{H},\mathrm{E}} $ were evaluated from thermodynamic analysis of surface tensions for the 1-decyl-3-methylimidazoulium bromide (C₁₀mimBr)–tetraethylene glycol monooctyl ether (C₈E₄) and 1-decyl-3-methyl-imidazolium tetrafluorobrorate (C₁₀mimBF₄)–C₈E₄ systems, where the counter anion of imidazolium salts is different from each other. The higher miscibility of two components compared to an ideal mixing and thus negative $ {\widehat{g}}^{\mathrm{H},\mathrm{E}} $ were observed in the former, which comes from the ion–dipole interaction between imidazolium cation and the oxyethylene group of C₈E₄. On the other hand, the lower miscibility and thus positive $ {\widehat{g}}^{\mathrm{H},\mathrm{E}} $ were observed for the latter. Such differences were attributed to that BF₄ ^? forms two hydrogen bonds and has stronger affinity with the cationic head group of C₁₀mim⁺ than Br^?. This results in that the ion–dipole interaction between C₈E₄ and C₁₀mim⁺ cation is diminished in the C₁₀mimBF₄–C₈E₄ system.     

Anisotropic Poisson Effect and Deformation-Induced Fluorescence Change of Elastic 9,10-Dibromoanthracene Single Crystals

Elastic organic crystals have attracted considerable attention as next-generation flexible smart materials. However, the detailed information on both molecular packing change and macroscopic mechanical crystal deformations upon applied stress is still insufficient. Herein, we report that fluorescent single crystals of 9,10-dibromoanthracene are elastically bendable and stretchable, which allows a detailed investigation of the deformation behavior. We clearly observed a Poisson effect for the crystal, where the short axes (b and c-axes) of the crystal are contracted upon elongation along the long axis (a-axis). Moreover, we found that the Poisson's ratios along the b-axis and c-axis are largely different. Theoretical molecular simulation suggests that the tilting motion of the anthracene may be responsible for the large deformation along the c-axis. Spatially resolved photoluminescence (PL) measurement of the bent elastic crystals reveals that the PL spectra at the outer (elongated), central (neutral), and inner (contracted) sides are different from each other.     

Spatiotemporal Dynamics of Aggregation-Induced Emission Enhancement Controlled by Optical Manipulation

We present spatiotemporal control of aggregation-induced emission enhancement (AIEE) of a protonated tetraphenylethene derivative by optical manipulation. A single submicrometer-sized aggregate is initially confined by laser irradiation when its fluorescence is hardly detectable. The continuous irradiation of the formed aggregate leads to sudden and rapid growth, resulting in bright yellow fluorescence emission. The fluorescence intensity at the peak wavelength of 540 nm is tremendously enhanced with growth, meaning that AIEE is activated by optical manipulation. Amazingly, the switching on/off of the activation of AIEE is arbitrarily controlled by alternating the laser power. This result means that optical manipulation increases the local concentration, which overcomes the electrostatic repulsion between the protonated molecules, namely, optical manipulation changes the aggregate structure. The dynamics and mechanism in AIEE controlled by optical manipulation will be discussed from the viewpoint of molecular conformation and association depending on the laser power.     

Anisotropic Poisson Effect and Deformation‐Induced Fluorescence Change of Elastic 9,10‐Dibromoanthracene Single Crystals

Elastic organic crystals have attracted considerable attention as next‐generation flexible smart materials. However, the detailed information on both molecular packing change and macroscopic mechanical crystal deformations upon applied stress is still insufficient. Herein, we report that fluorescent single crystals of 9,10‐dibromoanthracene are elastically bendable and stretchable, which allows a detailed investigation of the deformation behavior. We clearly observed a Poisson effect for the crystal, where the short axes (b and c‐axes) of the crystal are contracted upon elongation along the long axis (a‐axis). Moreover, we found that the Poisson's ratios along the b‐axis and c‐axis are largely different. Theoretical molecular simulation suggests that the tilting motion of the anthracene may be responsible for the large deformation along the c‐axis. Spatially resolved photoluminescence (PL) measurement of the bent elastic crystals reveals that the PL spectra at the outer (elongated), central (neutral), and inner (contracted) sides are different from each other.     

Presence of β-Turn Structure in Recombinant Spider Silk Dissolved in Formic Acid Revealed with NMR

Spider dragline silk is a biopolymer with excellent mechanical properties. The development of recombinant spider silk protein (RSP)-based materials with these properties is desirable. Formic acid (FA) is a spinning solvent for regenerated Bombyx mori silk fiber with excellent mechanical properties. To use FA as a spinning solvent for RSP with the sequence of major ampullate spider silk protein from Araneus diadematus, we determined the conformation of RSP in FA using solution NMR to determine the role of FA as a spinning solvent. We assigned ¹H, ¹³C, and ¹⁵N chemical shifts to 32-residue repetitive sequences, including polyAla and Gly-rich regions of RSP. Chemical shift evaluation revealed that RSP is in mainly random coil conformation with partially type II β-turn structure in the Gly-Pro-Gly-X motifs of the Gly-rich region in FA, which was confirmed by the ¹⁵N NOE data. In addition, formylation at the Ser OH groups occurred in FA. Furthermore, we evaluated the conformation of the as-cast film of RSP dissolved in FA using solid-state NMR and found that β-sheet structure was predominantly formed.     

Ir(III)‐Catalyzed C7‐Position‐Selective Oxidative CH Alkenylation of Indolines with Alkenes in Air

An efficient method for C7‐position‐selective alkenylation of N‐substituted indolines with alkenes is reported. Various 7‐alkenylindolines were obtained in moderate to excellent yields in air in the presence of catalytic amounts of [Cp*IrCl₂]₂, AgOTf, and Cu(OAc)₂. The protocol relies on the use of a carbonyl or carbamoyl group on the nitrogen atom of indoline as a directing group and is potentially applicable to the synthesis of 7‐alkenylindoles and 7‐alkylindoles.     

One‐Pot Synthetic Procedure for2,2′‐Disubstituted Biaryls via the Suzuki Coupling Reaction of Aryl Triflates in a Biphasic Solvent System

A one‐pot synthetic procedure for 2,2′‐disubstituted biaryls was developed via a Suzuki cross‐coupling reaction of aryl triflates in a biphasic solvent system. The effects of various bases and solvents were investigated. Results showed that the Na₂CO₃–toluene/H₂O combination gave the highest yields.