yrammuS 要概太田 裕道51Hiromichi OHTA舟橋 正浩52Masahiro FUNAHASHI半導体界面に蓄積された二次元電子ガスの熱電能電界変調 （2017採択）Electric field thermopower modulation of two-dimensional electron gas accumulated at semiconductor interface(Project 2017)イオン種を認識するナノ相分離型液晶性レドックス活性薄膜材料の創製とデバイス応用 （2017採択）Development of ion-responsive thin films based on nanosegregated liquid-crystalline redox-active materials and their device application(Project 2017)45Trifluoromethylated organic compounds have been gained much attention in the fields of pharmaceuticals, agrochemicals, and material sciences. In this research project, we developed a novel and efficient synthetic methods for the trifluoromethylated compounds using fluorocarbon, HFC23, and trifluoromethyl iodide. Trif-luoromethyl anion generated from HFC23 is very unstable to decompose into difluorocarbene and fluoride spontaneously. We overcame the issue by using the ion-pairing of trifluoromethyl anion with sterically de-manding organic superbase, P4- tBu, and realized the stereodivergent trifluoromethylation reactions. We also achieved the stabilization of trifluoromethyl anion by ion-paring with the complex of a potassium cation and glymes. Moreover, micro-flow trifluoromethylation using HFC23 was also developed. Photoredox trifluo-romethylations of alkenes and alkynes with trifluoromethyl iodide via sub-phthalocyanine and phthalocya-nine-catalysis were also developed.低次元化により電子状態密度が離散的になると熱電能が数倍に増強されるというDresselhaus理論（1993）は，熱電材料設計に有用と信じられているが，電子状態密度を二次元⇔三次元制御しながら，熱電能増強を実験的に検証した例はない．本研究では，超微細熱電材料用汎用熱電能計測装置を活用し，様々な絶縁体／半導体ヘテロ界面の二次元電子ガスをゲート電界によって蓄積／空乏させ，その電子状態密度を二次元⇔三次元制御し，その時の熱電能をゲート電界に対して連続的に計測することで，Dres-selhaus理論の実験的な検証を行った．その結果，二次元電子ガスは十分に薄いにも関わらず，AlGaN/GaN，BaSnO3，SnO2において熱電能の増強は見られず，熱電能はいずれも三次元的であった．Dresselhaus theory (1993), the thermopower can be enhanced by several times when the electronic density of states (DOS) becomes discrete upon low-dimensionalization, is believed as the effective way for the material design of thermoelectric materials. However, it has not been experimentally verified the thermopower en-hancement by modulating the DOS from two-dimensional (2D) to three-dimensional (3D) vice versa. In this study, the Dresselhaus theory was experimentally verified by measuring the thermopower using the thermo-power measuring equipment for tiny materials upon the gate electric field application to the insulator/semi-conductor heterointerface, which accumulates/depletes the 2DEG. The DOS was modulated from 2D to 3D vice versa. Although the effective thickness of the 2DEGs was enough thinner, it was found that the thermo-power enhancement did not occur and it seemed to be 3D in the case of AlGaN, BaSnO3, and SnO2.本研究課題ではアルカリ金属イオンなどのイオン種を認識し，共存する金属イオンの種類によって，電気伝導率や酸化還元電位が変化するナノ相分離型液晶性電気化学機能材料の創製を目的とし，アルカリ金属イオンを認識するクラウンエーテル部位，および，イミダゾリウム部位を導入した液晶性ペリレンビスイミド誘導体を合成した．クラウンエーテルを導入した液晶材料においては，LiOTf, および，NaOTfと高濃度で液晶性錯体を形成した．液晶相は錯体を形成することにより安定化された．イミダゾリウムRep. Grant. Res., Asahi Glass Foundation (2020)
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