Development of New Responsive Molecules Showing Piezo-pH Change and/or Piezochromism

开发显示压电 pH 变化和/或压致变色现象的新型响应分子

• 批准号: 06650981
• 负责人: MIKI Sadao
• 金额: $ 1.34万
• 依托单位: Kyoto Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06650981/
• 关键词: responsiveness; piezochromism; acidity; photochromism; electrochromism

Stimulus responsive molecules have been a subject of much recent interest because of their potentiality in wide range of material science. In this context, development of new responsive molecules of varieties with respect to the kinds of input-stimuli as well as properties responding to them. In this research project, several new responsive molecules have been synthesized, which showed responsivities such as piezo-pH,piezochromism, photo-pka, photochromism, as follows. 3,6-Dimitrothioxanthene-10,10-dioxide and 3-cyano-6-nitrothioxanthene-10,10-dioxide showed piezochromism upon pressing to give rise to color developing. The mechanism of the piezochromism has been studied in detail, that is, the conjugate base formed by the C (9) -H dissociation gave the color. This system changes the degree of the proton dissociation responding to pressure, and the phenomenon is closely relevant to piezo-pH change. This idea has been extended to light regulation of molecular acidity pka. It was intended … More to control the acidity of thioxanthene-10-10-dioxide by the light-driven structural change of a photoresponsive substituent introduced to the molecular skeleton. Thus, 3-methoxycarbonyl-6-trans-phenylazothioxanthene-10-10-dioxide and 3-methoxycarbonyl-6-trans-phenylazothioxanthene-10-10-dioxide were synthesized. The phenylazo group showed reversible trans/cis photo-isomerization, and the molecules of the trans form revealed much larger acidity than the cis-form. It has been intended to extend the light-driven property changes to the Redox potentials of a molecule. For this purpose, tri-butyl-polyacenequinones were synthesized. They undergo reversible photoisomerization between the corresponding valene isomer. The isomerizations are accompanied by large change in the pai-electronic structure, and as a result, are accompanied by large change in the Redox potential of the molecules. It was well known that the C60 possess an unique responsivity towards light. In order to materialize the property, it should be important to fix the molecule to solid materials. In this context, a new method for making C-C bond to C60 has been developed. Less

刺激响应分子由于其在材料科学中的广泛应用而成为近年来研究的热点。在这种情况下，开发新的响应分子的品种相对于输入刺激的种类以及响应于它们的属性。本课题合成了几种新型的响应分子，它们具有压电pH、压致变色、光pka、光致变色等响应特性。3，6-二硝基噻吨-10，10-二氧化物和3-氰基-6-硝基噻吨-10，10-二氧化物在压制时显示压致变色，从而引起显色。详细研究了其压致变色机理，即C（9）-H离解形成的共轭碱使其呈现颜色。该体系的质子解离程度随压力的变化而变化，这一现象与压力-pH的变化密切相关。这个想法已经扩展到分子酸度pka的光调节。它的目的 ...更多信息 通过引入分子骨架的光响应取代基的光驱动结构变化来控制噻吨-10-10-二氧化物的酸性。合成了3-甲氧羰基-6-反式-苯基偶氮噻吨-10-10-二氧化物和3-甲氧羰基-6-反式-苯基偶氮噻吨-10-10-二氧化物。苯基偶氮基团表现出可逆的反式/顺式光异构化，并且反式形式的分子显示出比顺式形式大得多的酸性。它旨在将光驱动的性质变化扩展到分子的氧化还原电位。为此，合成了三丁基聚苯醌。它们在相应的缬烯异构体之间进行可逆的光异构化。异构化伴随着对电子结构的大变化，因此，伴随着分子的氧化还原电位的大变化。众所周知，C60对光具有独特的响应性。为了实现这种性质，将分子固定在固体材料上是很重要的。在此背景下，开发了一种使C-C键连接到C60的新方法。少

项目成果

S. Miki: "Introduction of Two Benzyl Groups to C60 by Using the Collman Reagent" Tetrahedron Lett.34(印刷中). (1996)

S. Miki：“使用 Collman 试剂将两个苄基引入 C60”Tetrahedron Lett.34（出版中）。

R.M.El-Shishtawy: "Synthesis and Photoreaction of 4, 5, 7-Tri-t-butylbenzo[c]thiophene:A Novel Benzd[c]thiophene Derivative and Its Dewar Isomer," Tetrahedron Lett.33. 3177-3180 (1995)

R.M.El-Shishtawy：“4,5,7-三叔丁基苯并[c]噻吩的合成和光反应：一种新型苯并[c]噻吩衍生物及其杜瓦异构体”，Tetrahedron Lett.33。

R.M.El-Shishtawy, K.Fukunishi, and S.Miki: "Synthesis and Photoreaction of 4,5,7-Tri-butylbenzo [c] thiophene : A Novel Benzo [c] thiophene Derivative and Its Dewar Isomer." Tetrahedron Lett.Vol.33. 3177-3180 (1995)

R.M.El-Shishtawy、K.Fukunishi 和 S.Miki：“4,5,7-三丁基苯并[c]噻吩的合成和光反应：一种新型苯并[c]噻吩衍生物及其杜瓦异构体。”

S.Miki: "Synthesis of 1, 2, 3-Tri-t-buty1-6, 13- and 8,9,10-tri-t-butyl-5, 14-pentasenequinones and Their Photochromic Behaviors:New Photochromic Molecules" Tetrahedron. 53. 4269-4276 (1996)

S.Miki：“1,2,3-三叔丁基1-6,13-​​和8,9,10-三叔丁基-5,14-五烯醌的合成及其光致变色行为：新型光致变色分子”

H. Dodiuk: "Structure of Cyclodextrins and of Their Complexes. Chromatographic and NMR Study of 1,2,3-Tri-t-butyl-naphthalene and Its Complex with gamma-cyclodextrin." Tetrahedron. 50. 3619-3626 (1994)

H. Dodiuk：“环糊精及其复合物的结构。1,2,3-三叔丁基萘及其与 γ-环糊精的复合物的色谱和核磁共振研究。”