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

由于刺激反应分子在材料科学的广泛领域中的潜力，近年来一直是人们感兴趣的主题。在此背景下，发展新的响应分子的种类与输入刺激的种类以及对它们的响应特性。在本研究项目中，我们合成了几种新型的响应性分子，它们表现出如下的响应性：pH压电性、压电性、光致变色性、光致变色性。3，6-二甲基硫杂菲-10，10-二氧化物和3-氰基-6-硝基硫杂菲-10，10-二氧化物在压制时表现出压电致变色作用，从而产生显色。详细研究了压电致变色的机理，即C(9)-H解离形成的共轭碱给出了颜色。该体系改变了质子解离对压力的响应程度，这一现象与压电态pH的变化密切相关。这个想法已经扩展到对分子酸性PKA的光调节。它的目的是…更重要的是，通过在分子骨架上引入光响应取代基的光驱动结构变化来控制硫杂菲-10-10-二氧化物的酸性。从而合成了3-methoxycarbonyl-6-trans-phenylazothioxanthene-10-10-dioxide和3-methoxycarbonyl-6-trans-phenylazothioxanthene-10-10-dioxide。苯偶氮基表现出可逆的反式/顺式光异构化反应，反式分子的酸性远大于顺式分子。它的目的是将光驱动的性质变化扩展到分子的氧化还原电势。为此，合成了三丁基聚苯二酮。它们在相应的Valene异构体之间进行可逆光异构化。异构化伴随着分子的多电子结构的大变化，从而伴随着分子的氧化还原电势的大变化。众所周知，C60对光具有独特的响应性。为了实现这一性质，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键与C60成键的新方法。较少

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