アタラシイ カンジョウ カゴウブツ ノ カガク ト ソノ ゴウセイテキ オウヨウ ニ カンスル ケンキュウ

京都大学0048新制・論文博士工学博士乙第2869号論工博第812号新制||工||318(附属図書館)UT51-50-I137(主査)教授 野崎 一, 教授 河西 三省, 教授 庄野 達哉学位規則第5条第2項該当Kyoto UniversityDFA

Nickel-catalyzed carbocyanation of alkynes

Nickel-catalyzed carbocyanation reaction of alkynes is described. Alkynes undergo aryl- and allylcyanation reaction in the presence of nickel-phosphine catalysts to give a wide range of substituted acrylonitriles in highly stereo-, regio-, and chemoselective manners. Lewis acid cocatalysts, such as AlMe3, AlMe2Cl, and BPh3, are found to promote the arylcyanation significantly. The cooperative catalysis of nickel and Lewis acid also allows the carbocyanation reaction using alkenyl and alkyl cyanides

Twisting strategy applied to N,N-diorganoquinacridones leads to organic chromophores exhibiting efficient solid-state fluorescence

A new molecular design of organic emitters exhibiting efficient solid-state fluorescence, which involves planarity breaking of N, N-diorganoquinacridones, is presented. The new design principle led to the development of dimethyl 2, 5-diaminoterephthalates and 2, 5-diamino-1, 4-diaroylbenzenes, which emitted green to yellow and yellow to red light with high-to-excellent quantum yields, respectively. In addition, the photoluminescence properties of the diaroylbenzenes were dependent on the morphology and reversibly variable by thermal and solvent vapor stimuli

Synthesis and Photophysical Properties of 2,3,5,6,7,8-Hexasilabicyclo[2.2.2]octan-1-yl-substituted Arenes

Incorporation of 2, 2, 3, 3, 5, 5, 6, 6, 7, 7, 8, 8-dodecamethyl-2, 3, 5, 6, 7, 8-hexasilabicyclo[2.2.2]octan-1-yl moiety into such chromophores as biphenyl, terphenyl, stilbene, and tolan was found to induce bathochromic shifts of absorption and fluorescence spectra, compared with those of the parent chromophores. Moreover, enhancement of the molar extinction coefficients and the fluorescence quantum yields by the substitution was also observed. These results indicate that σ–π conjugation between the polysilacage moiety and the chromophores is operative. Theoretical study of the polysilacage-substituted chromophores is also presented