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Novel local D-A interactions and physical properties in organic mixed crystals

有机混合晶体中新颖的局域 D-A 相互作用和物理性质

基本信息

批准号：
13640579
负责人：
HASHIMOTO Masao
金额：
$ 2.18万
依托单位：
Kobe University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

项目摘要

Local D-A interactions and some physical-chemical properties in mixed crystals of organic compounds were investigated. The materials studies were derivatives of triptycene, azulene, 4-substitutedbenzyl alcohols and alkyl urea.A new method of preparation of triptycenequinone (TPQ)/triptycenehydroquinone (TPHQ) mixed crystal was found. Crystal structures were determined for bis-(Bromomethyl)triptycene (bis-BrMe-TPQ) and its several clathrates. A mixed crystal of the compound with bis-(bromomethyl)triptycenehydroquinone (bis-BrMe-TPHQ) exhibited local D-A interaction.Four membered ring type H-bond systems and phase transition were found for bis-(hydroxy)triptycenes. From the knowledge of the crystal structure, an interesting dielectric property is expected for its mixed crystal with hydroxytriptycene.The crystal structure of 6,7-dimethoxytriptycene suggests that it cannot form a TPQ/TPHQ type mixed crystal. X-ray structure of 5,12-dihydro-o-5,12-benzenonaphthacne-1,4-dione revealed the presence of its clathrate with benzene and this result indicates that a local D-A interaction in a mixed crystal would be possible by changing the guest from benzene to other methyl-benzenes.For mixed crystals of p-substitutedbenzyl alcohols, composition dependence of the characteristics of the phase transitions, as well as an isotope effect on the transition behavior, were investigated in detail. These results contributed to elucidate the transition mechanism of the compounds.Among a series of alkyl-ures, octyl-urea exhibited a novel phase transition accompanied by a very large enthalpy change. Mixed crystals of octyl- and heptyl-urea were found to show a transition characteristic that was very dependent on the composition, giving useful information on the transition mechanism.

本文研究了有机化合物混晶中的局域D-A相互作用和某些物理化学性质。以三蝶烯衍生物、甘菊环、4-取代苯甲醇和烷基脲为原料，探索了一种制备三蝶烯醌（TPQ）/三蝶烯对苯二酚（TPHQ）混晶的新方法，测定了双-（溴甲基）三蝶烯（bis-BrMe-TPQ）及其几种包合物的晶体结构。该化合物与双溴甲基三蝶烯对苯二酚（bis-BrMe-TPHQ）的混晶显示出局部的D-A相互作用，双羟基三蝶烯存在四元环型氢键体系和相变。从晶体结构上看，6，7-二甲氧基三蝶烯与羟基三蝶烯的混晶具有很好的介电性能，其晶体结构表明它不能形成TPQ/TPHQ型混晶。通过对5，12-二氢-邻-5，12-苯并萘-1，4-二酮的X-射线结构的研究，发现其与苯的包合物的存在，表明通过将客体从苯转变为其它甲苯，混晶中可能存在局部的D-A相互作用。以及同位素效应的转变行为进行了详细的研究。这些结果有助于阐明化合物的相变机理，在一系列烷基脲中，辛基脲表现出一种新的相变，并伴有很大的焓变。发现辛基-和庚基-脲的混合晶体显示出非常依赖于组合物的过渡特性，提供了关于过渡机制的有用信息。