小分子を内包した開口フラーレンC60誘導体の合成と性質

京都大学0048新制・課程博士博士(工学)甲第20396号工博第4333号新制||工||1671(附属図書館)京都大学大学院工学研究科物質エネルギー化学専攻(主査)教授 村田 靖次郎, 教授 辻 康之, 教授 中村 正治学位規則第4条第1項該当Doctor of Philosophy (Engineering)Kyoto UniversityDFA

Synthesis and Structure of an Open-Cage Thiafullerene C₆₉S: Reactivity Differences of an Open-Cage C₇₀ Tetraketone Relative to Its C₆₀ Analogue

An open-cage C₇₀ fullerene with a 13-membered ring-opening and a bis­(hemiacetal) moiety was synthesized by the reaction of the corresponding open-cage C₇₀ diketone with nucleophilic oxidizing agents. The size of the cage opening could be expanded by a subsequent dehydration reaction. Reaction of the thus obtained open-cage C₇₀ tetraketone with elemental sulfur in the presence of tetrakis­(dimethylamino)­ethylene resulted in the formation of the first example of an open-cage C₆₉S thiafullerene with a 12-membered ring-opening. The formation of this sulfur-containing heterofullerene reflects a significantly different chemical reactivity for the open-cage C₇₀ tetraketone relative to its C₆₀ analogue. The structures of all novel compounds were unambiguously determined by single crystal X-ray diffraction analyses, in addition to which the electrochemical properties of the thiafullerene C₆₉S were examined and compared with those of the corresponding C₇₀ analogue

Synthesis and Structure of an Open-Cage Thiafullerene C₆₉S: Reactivity Differences of an Open-Cage C₇₀ Tetraketone Relative to Its C₆₀ Analogue

An open-cage C₇₀ fullerene with a 13-membered ring-opening and a bis­(hemiacetal) moiety was synthesized by the reaction of the corresponding open-cage C₇₀ diketone with nucleophilic oxidizing agents. The size of the cage opening could be expanded by a subsequent dehydration reaction. Reaction of the thus obtained open-cage C₇₀ tetraketone with elemental sulfur in the presence of tetrakis­(dimethylamino)­ethylene resulted in the formation of the first example of an open-cage C₆₉S thiafullerene with a 12-membered ring-opening. The formation of this sulfur-containing heterofullerene reflects a significantly different chemical reactivity for the open-cage C₇₀ tetraketone relative to its C₆₀ analogue. The structures of all novel compounds were unambiguously determined by single crystal X-ray diffraction analyses, in addition to which the electrochemical properties of the thiafullerene C₆₉S were examined and compared with those of the corresponding C₇₀ analogue

Synthesis and Structure of an Open-Cage Thiafullerene C₆₉S: Reactivity Differences of an Open-Cage C₇₀ Tetraketone Relative to Its C₆₀ Analogue

An open-cage C₇₀ fullerene with a 13-membered ring-opening and a bis­(hemiacetal) moiety was synthesized by the reaction of the corresponding open-cage C₇₀ diketone with nucleophilic oxidizing agents. The size of the cage opening could be expanded by a subsequent dehydration reaction. Reaction of the thus obtained open-cage C₇₀ tetraketone with elemental sulfur in the presence of tetrakis­(dimethylamino)­ethylene resulted in the formation of the first example of an open-cage C₆₉S thiafullerene with a 12-membered ring-opening. The formation of this sulfur-containing heterofullerene reflects a significantly different chemical reactivity for the open-cage C₇₀ tetraketone relative to its C₆₀ analogue. The structures of all novel compounds were unambiguously determined by single crystal X-ray diffraction analyses, in addition to which the electrochemical properties of the thiafullerene C₆₉S were examined and compared with those of the corresponding C₇₀ analogue

Synthesis and Structure of an Open-Cage Thiafullerene C₆₉S: Reactivity Differences of an Open-Cage C₇₀ Tetraketone Relative to Its C₆₀ Analogue

An open-cage C₇₀ fullerene with a 13-membered ring-opening and a bis­(hemiacetal) moiety was synthesized by the reaction of the corresponding open-cage C₇₀ diketone with nucleophilic oxidizing agents. The size of the cage opening could be expanded by a subsequent dehydration reaction. Reaction of the thus obtained open-cage C₇₀ tetraketone with elemental sulfur in the presence of tetrakis­(dimethylamino)­ethylene resulted in the formation of the first example of an open-cage C₆₉S thiafullerene with a 12-membered ring-opening. The formation of this sulfur-containing heterofullerene reflects a significantly different chemical reactivity for the open-cage C₇₀ tetraketone relative to its C₆₀ analogue. The structures of all novel compounds were unambiguously determined by single crystal X-ray diffraction analyses, in addition to which the electrochemical properties of the thiafullerene C₆₉S were examined and compared with those of the corresponding C₇₀ analogue

Expansion of Orifices of Open C₆₀ Derivatives and Formation of an Open C₅₉S Derivative by Reaction with Sulfur

The reaction of a tetraketo-open-cage C₆₀ derivative with elemental sulfur in the presence of tetrakis(dimethylamino)ethylene afforded novel open C₆₀ derivatives containing sulfur atom(s) in the rim of the orifice and the first example of an open C₅₉S derivative. The single crystal X-ray analyses clearly determined these structures and demonstrated that a water molecule was encapsulated inside the cages. The orifice sizes and electronic properties of these fullerene derivatives were revealed

Synthesis and Structure of an Open-Cage Thiafullerene C₆₉S: Reactivity Differences of an Open-Cage C₇₀ Tetraketone Relative to Its C₆₀ Analogue

An open-cage C₇₀ fullerene with a 13-membered ring-opening and a bis­(hemiacetal) moiety was synthesized by the reaction of the corresponding open-cage C₇₀ diketone with nucleophilic oxidizing agents. The size of the cage opening could be expanded by a subsequent dehydration reaction. Reaction of the thus obtained open-cage C₇₀ tetraketone with elemental sulfur in the presence of tetrakis­(dimethylamino)­ethylene resulted in the formation of the first example of an open-cage C₆₉S thiafullerene with a 12-membered ring-opening. The formation of this sulfur-containing heterofullerene reflects a significantly different chemical reactivity for the open-cage C₇₀ tetraketone relative to its C₆₀ analogue. The structures of all novel compounds were unambiguously determined by single crystal X-ray diffraction analyses, in addition to which the electrochemical properties of the thiafullerene C₆₉S were examined and compared with those of the corresponding C₇₀ analogue

Expansion of Orifices of Open C₆₀ Derivatives and Formation of an Open C₅₉S Derivative by Reaction with Sulfur

The reaction of a tetraketo-open-cage C₆₀ derivative with elemental sulfur in the presence of tetrakis(dimethylamino)ethylene afforded novel open C₆₀ derivatives containing sulfur atom(s) in the rim of the orifice and the first example of an open C₅₉S derivative. The single crystal X-ray analyses clearly determined these structures and demonstrated that a water molecule was encapsulated inside the cages. The orifice sizes and electronic properties of these fullerene derivatives were revealed