Tsuyoshi Michinobu

Abstract A wide variety of monomeric and oligomeric, donor‐substituted 1,1,4,4‐tetracyanobutadienes (TCBDs) have been synthesized by [2+2] cycloaddition between tetracyanoethylene (TNCE) and donor‐substituted alkynes, followed by electrocyclic ring opening of the initially formed cyclobutenes. Reaction yields are often nearly quantitative but can be affected by the electron‐donating power and steric demands of the alkyne substituents. The intramolecular charge‐transfer (CT) interactions between

Donor-acceptor molecules with 4-(dimethylamino)phenyl donor and 1,1,4,4-tetracyanobuta-1,3-diene acceptor moieties are readily prepared by short, high-yielding routes. The quite small chromophores are characterised by X-ray crystallography and feature intense intramolecular charge-transfer bands, substantial quinoid character in the donor rings, reversible electrochemical reductions and oxidations and powerful third-order optical nonlinearities.

Electron-deficient building blocks based on benzothiadiazole and its π-extended, heteroannulated derivatives for constructing high-performance semiconducting polymers are described.

The development of high-performance unipolar n-type semiconducting polymers still remains a significant challenge. Only a few examples exhibit a unipolar electron mobility over 5 cm² V^-1 s^-1. In this study, a series of new poly(benzothiadiazole-naphthalenediimide) derivatives with a high unipolar electron mobility (μ_e) up to 7.16 cm² V^-1 s^-1 in thin-film transistors are reported. The dramatically increased μ_e

Monolayers of the cholesterol-armed cyclen Na+ complex at the air-water interface display a remarkable, surface pressure dependent enantioselectivity of amino acid recognition. Upon compression of the monolayer, the binding constants of amino acids increase accompanying an inversion of chiral selectivity from the d- to l-form in the case of valine.

The [2+2] cycloaddition-retroelectrocyclization (CA-RE) reaction between electron-rich alkynes and electron-deficient alkenes is an efficient procedure to create nonplanar donor-acceptor (D-A) chromophores in both molecular and polymeric platforms. They feature attractive properties including intramolecular charge-transfer (ICT) bands, nonlinear optical properties, and redox activities for use in next-generation electronic and optoelectronic devices. This Review summarizes the development of the

Room temperature liquid C60 derivatives bearing a 2,4,6-trialkyloxyphenyl branch show a dramatic decrease in viscosity with an increase in the length of the alkyl chains. This feature, when combined with electrochemical activities similar to those of pristine C60 and relatively high charge carrier mobility, makes them an extremely attractive novel carbon material for future applications in materials science.

While high-performance p-type semiconducting polymers are widely reported, their n-type counterparts are still rare in terms of quantity and quality. Here, an improved Stille polymerization protocol using chlorobenzene as the solvent and palladium(0)/copper(I) as the catalyst is developed to synthesize high-quality n-type polymers with number-average molecular weight up to 10⁵ g mol^-1 . Furthermore, by sp² -nitrogen atoms (sp² -N) substitution, three n

After the historical development from the insoluble polyacetylene film to soluble and processible aromatic polymers, donor-acceptor-type aromatic polymers have recently emerged as a new class of semiconducting polymers. The polymer energy levels and band gaps can be tuned by the appropriate selection of the donor and acceptor moieties, and some of these polymers showed good optoelectronic or photovoltaic performances. The conventional synthetic method for achieving donor-acceptor-type aromatic p

A quantitative addition reaction between aromatic amino-substituted alkynes and tetracyanoethylene (TCNE), yielding donor-substituted tetracyanobutadiene chromophores, was for the first time employed as a click-type reaction to improve the thermal and optoelectronic properties of aromatic polyamines. The first reduction potentials or the LUMO levels of the aromatic polyamines were found to linearly decrease by the stepwise TCNE addition.

High‐mobility semiconducting polymers composed of arylene vinylene and dithiophene‐thiadiazolobenzotriazole (SN) units are developed by three powerful design strategies, namely, backbone engineering, heteroatom substitution, and side‐chain engineering. First, starting from the quaterthiophene‐SN copolymer, a vinylene spacer is inserted into the quaterthiophene unit for constructing highly‐planar backbones. Second, heteroatoms (O and N atoms) are incorporated into the thienylene vinylene moieties

The direct arylation polycondensation (DArP) appeared as an efficient method for producing semiconducting polymers but often requires acceptor monomers with orienting or activating groups for the reactive carbon-hydrogen (C-H) bonds, which limits the choice of acceptor units. In this study, we describe a DArP for producing high-molecular-weight all-acceptor polymers composed of the acceptor monomers without any orienting or activating groups via a modified method using Pd/Cu co-catalysts. We thu

The molecular structure of polymer electrets is crucial for creating diverse functionalities of organic field-effect transistor (OFET) devices. Herein, a conceptual framework has been applied in this study to design the highly photoresponsive carbazole-based copolymer electret materials for the application of photoresponsive OFET memory. As an electret layer, two 1,8-carbazole-based copolymers were utilized; the <b>copoly(CT)</b> consisted of carbazole as the donor group and thiophene as the π-s

ADVERTISEMENT RETURN TO ISSUECommunication to the...Communication to the EditorNEXTOne-Step Synthesis of Donor−Acceptor type Conjugated Polymers from Ferrocene-Containing Poly(aryleneethynylene)sTsuyoshi Michinobu*†‡, Hiroe Kumazawa§, Keiichi Noguchi§, and Kiyotaka Shigehara§View Author Information† Global Edge Institute, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8550, Japan‡ PRESTO, Japan Science and Technology Agency (JST), Kawaguchi, Saitama, Japan§ Graduate School of Engi

Abstract Fine‐tuning of the charge carrier polarity in organic transistors is an important step toward high‐performance organic complementary circuits and related devices. Here, three new semiconducting polymers, namely, pDPF‐DTF2, pDPSe‐DTF2, and pDPPy‐DTF2, are designed and synthesized using furan, selenophene, and pyridine flanking group‐based diketopyrrolopyrrole cores, respectively. Upon evaluating their electrical properties in transistor devices, the best performance has been achieved for