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Research on visible-light photocatalysts of metal nanoparticles (NPs) has focused on increasing the reactant conversion by light-excited charges (electrons and positively charged holes). However, light irradiation can accelerate catalysis by other mechanisms. Here, we report that 650 nm wavelength irradiation of 0.75 W·cm-2 significantly increases nitrile yield of ammoxidation of primary aromatic alcohols with an ammonium salt over supported Pd NPs at 80 °C in air. We found that the desorption of the nitrile product from the catalyst is the rate-determining step; the irradiation promotes not only alcohol oxidation and subsequent aldehyde cyanation over the Pd NPs but also the nitrile desorption selectively via resonance energy transfer to achieve a high nitrile yield. This new mechanism provides a knob for the exquisite control of catalytic reaction pathways for ecofriendly synthesis.

Surface-plasmon-mediated phenylacetylide intermediate transfer from the Cu to the Pd surface affords a novel mechanism for transmetalation, enabling wavelength-tunable cross-coupling and homo-coupling reaction pathway control. C−C bond forming Sonogashira coupling and Glaser coupling reactions in O2 atmosphere are efficiently driven by visible light over heterogeneous Cu and Pd nanoparticles as a mixed catalyst without base or other additives. The reaction pathway can be controlled by switching the excitation wavelength. Shorter wavelengths (400–500 nm) give the Glaser homo-coupling diyne, whereas longer wavelength irradiation (500–940 nm) significantly increases the degree of cross-coupling Sonogashira coupling products. The ratio of the activated intermediates of alkyne to the iodobenzene is wavelength dependent and this regulates transmetalation. This wavelength-tunable reaction pathway is a novel way to optimize the product selectivity in important organic syntheses.

identifier:oai:t2r2.star.titech.ac.jp:50637732

identifier:oai:t2r2.star.titech.ac.jp:50637723

Blue-color-emitting organic semiconductors are of significance for organic light-emitting diodes (OLEDs). In this study, through Suzuki coupling polymerization, three 1,4-naphthalene-based copolymers—namely, PNP(1,4)-PT, PNP(1,4)-TF, and PNP(1,4)-ANT—were designed and synthesized. The variation of comonomers, phenothiazine (PT), triphenylamine substituted fluorene (TF), and anthanthrene (ANT), effectively tuned the emitting color and device performance of poly(9-vinyl carbazole) (PVK)-based OLEDs. Especially, the polymer PNP(1,4)-TF, bearing perpendicular aryl side groups, showed a most twisted structural geometry, which enabled an ultra-high thermal stability and a best performance with blue emitting in PVK-host-based OLEDs. Overall, in this work, we demonstrate a promising blue-color-emitting polymer through structural geometry manipulation.

Rigid, freestanding covalent organic framework (COF-1) membranes have been synthesized from 1,4-benzenediboronic acid (BDBA) precursors using two different approaches: room temperature solvent-vapour annealing (SVA) and solvothermal annealing (SA). Characterization of films using Fourier-transform infrared (FTIR) spectroscopy, x-ray diffraction (XRD), and various microscopies shows that the films obtained through the two different routes vary in their retained BDBA proportion, crystal size and macroscale morphology. Gas adsorption measurements give specific surface areas of 579 7 m2 g-1 and 739 11 m2 g-1 respectively, suggesting that the average porosity of these films is competitive with bulk-synthesized COF-1 particles. The films have a stratified structure, with a dense, thin top layer and a thicker, sponge-like base layer. Using nanoindentation, we measured the Young's modulus at the top surface of the SVA and SA films to be 3.64 1.20 GPa and 3.33 0.12 GPa respectively, with the smaller uncertainty for the SA film attributed to a more uniform morphology. These measurements provide useful experimental data pertaining to COF-1 mechanical properties, furnishing information relevant to the use of these free-standing membranes in applications such as gas filtration or storage.

The increasing interest in organic electrochemical transistors (OECTs) for next-generation bioelectronic applications motivates the design of novel conjugated polymers with good electronic and ionic transport. Many conjugated polymers developed for organic field-effect transistors (OFETs) exhibit high charge carrier mobilities but they are not suitable for OECTs due to poor ion-uptake arising from the non polar alkyl chain substituted on the conjugated backbone. They are also sensitive to moisture, resulting in poor performance in aqueous electrolytes. Herein, the widely used conjugated building block diketopyrrolopyrrole (DPP) is used and functionalized it with polar triethylene glycol side chains (PTDPP-DT) to promote ion penetration. The electrical performance of PTDPP-DT based OECT in two types of aqueous electrolytes is studied and the electrochemical doping response is investivated. It is found that the tetrafluoroborate (BF4−) anion with large crystallographic radius allows high-efficiency electrochemical doping of the PTDPP-DT polymer, and thus gives rise to the high transconductance of 21.4 ± 4.8 mS with good device stability, where it maintained over 91 % of its doped-state drain current after over 500 cycles of pulse measurement.

Studying multi-purpose applications of a specific material is a challenging topic in the organic electronics community. In this work, through molecular engineering and smart device structure design strategy, high performance in transistors and thin film display devices is simultaneously achieved by applying a simple new dye molecule, naphthalene flanked diketopyrrolopyrrole (DPPN), as the active layer material. Short alkyl chains (hexyl or octyl side groups for H-DPPN and O-DPPN, respectively) are adapted to improve the hole mobility in organic thin film transistors (OTFTs) and single crystal transistors (SCTs). Specifically, H-DPPN shows a similar hole mobility in either OTFTs or SCTs, while O-DPPN exhibits a dramatically enhanced mobility, reaching 0.125 cm2 V−1 s−1 in SCTs. Additionally, a smart organic light emitting diode (OLED) device is designed by using DPPN molecule as the dopant with a host matrix. The promising external quantum efficiencies of 4.0% and 2.3% are achieved for H-DPPN and O-DPPN fabricated OLEDs. Overall, in this work, it is reported that DPP-based small molecules can simultaneously function well in both transistors and thin film displays with high device performance through molecular and smart device engineering.