Synthesis and Response toward External Stimulli of Bithiophene Derivatives Bridged by Spirodienone Structure

螺环二烯酮结构桥连联噻吩衍生物的合成及其对外界刺激的响应

• 批准号: 20550039
• 负责人: KURATA Hiroyuki
• 金额: $ 2.75万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2008
• 资助国家: 日本
• 起止时间: 2008 至 2010
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-20550039/
• 关键词: チオフェン; 分子スイッチング; 酸化還元系; メカノクロミズム; スピロ構造; アモルファス; ビラジカル; 粉末X線回折; ジスピロ構造; 合成化学; 分子機械; 分子スイッチ; サイクリックボルタンメトリー

Bithiophene derivtives bridged with a bis (spirodienone) unit were synthesized and characterized. Palladium-catalyzed cross-coupling reactions with bromides afforded a variety of pi-extended derivatives. In these compounds, bond breaking and formation under redox conditions were observed by cyclic voltammetry (CV). Especially, 2,2'-bridged-3,3'-bithiophene derivatives showed significant temperature- and scan rate-dependence on CV. These phenomena indicate the existence of the equilibrium between dispiro-compounds and open-ring biradicals. Furthermore, mechanochromism, N,N-dialkylaminophenyl-substituted 2,2'-bridged-3,3'-bithiophene derivatives showed mechanochromism. During grinding the crystals, the color was changed from yellow to reddish orange, and by exposure to organic solvents, the reddish-orange color was immediately turned back to yellow.

合成并表征了以双螺二烯酮为桥连单元的联噻吩衍生物。钯催化的交叉偶联反应与溴化物提供了各种π-扩展的衍生物。在这些化合物中，通过循环伏安法（CV）观察到在氧化还原条件下的键断裂和形成。特别地，2，2 '-桥连-3，3'-联噻吩衍生物对CV显示出显著的温度和扫描速率依赖性。这些现象表明双螺环化合物和开环双自由基之间存在平衡。此外，机械变色，N，N-二烷基氨基苯基取代的2，2 ′-桥连-3，3 ′-联噻吩衍生物显示机械变色。在研磨晶体期间，颜色从黄色变为红橙子，并且通过暴露于有机溶剂，红橙子颜色立即变回黄色。

项目成果

Resonance Balance Shift in π-π One-Dimensional Chain of Delocalized Singlet Biradical

离域单重态双自由基π-π一维链中的共振平衡位移

• 发表时间: 2009
• 期刊: Angewandte Chemie, International Edition 48
• 作者: T.Kawase;A.Konishi;Y.Hirao;K.Matsumoto;H.Kurata;T.Kubo;山本幸明・田中賢治・高木隆吉・大方勝男・安倍学;Akihiro Shimizu
• 通讯作者: Akihiro Shimizu

8,14,30,36-Tetramethoxy[2.0.2.0](1,6) naphthalenophane-1,19-diyne : A Double-Helically Twisted Cyclophane by Diastereoselective Dimerization.

8,14,30,36-四甲氧基[2.0.2.0](1,6)萘芬-1,19-二炔：通过非对映选择性二聚形成双螺旋扭曲环芳。

• 发表时间: 2008
• 期刊: Chemistry- An Asian Journal 3(3)
• 作者: T.Kawase;T.Nakamura;K.Utsumi;K.Matsumoto;H.Kurata;M.Oda
• 通讯作者: M.Oda

An Extremely Simple Dibenzopentalene Synthesis from 2-Bromo-1-ethynylbenzenes Using Nickel(0) Complexes: Construction of Its Derivatives with Various Functionalities

• DOI: 10.1002/chem.200802471
• 发表时间: 2009-01-01
• 期刊: CHEMISTRY-A EUROPEAN JOURNAL
• 影响因子: 4.3
• 作者: Kawase, Takeshi;Konishi, Akihito;Kubo, Takashi
• 通讯作者: Kubo, Takashi

Resonance Balance Shift in π-π One-Dimensional Chain of Delocalized Singlet Biradical.

离域单重态双自由基 π-π 一维链中的共振平衡位移。

• 发表时间: 2009
• 期刊: Angewandte Chemie, International Edition 48(30)
• 作者: A.Shimizu;M.Uruichi;K.Yakushi;H.Matsuzaki;H.Okamoto;M.Nakano;Y.Hirao;K.Matsumoto;H.Kurata;T.Kubo
• 通讯作者: T.Kubo

An Extremely Simple Dibenzopentalene Synthesis from2-Bromo-1-ethynylbenzenes Using Nickel(O)Complexes : Construction ofIts Derivatives with Various Functionalities

使用镍（O）配合物从 2-溴-1-乙炔基苯极其简单地合成二苯并戊二烯：构建具有各种功能的其衍生物

• 发表时间: 2009
• 期刊: Chemistry-A European Journal 15
• 作者: T.Kawase;A.Konishi;Y.Hirao;K.Matsumoto;H.Kurata;T.Kubo;山本幸明・田中賢治・高木隆吉・大方勝男・安倍学;Akihiro Shimizu;近藤広理・井上祐太・藤井絵美・高木隆吉・大方勝男;Takeshi Kawase;井形直央・山本和弘・高木隆吉・小島聡志;川瀬 毅;川瀬 毅
• 通讯作者: 川瀬 毅