Research of Plastic-like crystalline phases and thermal properties of urea and thiourea derivatives with long chain alkyl groups

长链烷基脲及硫脲衍生物的类塑料晶相及热性能研究

• 批准号: 15550119
• 负责人: YAMAMURA Kimiaki
• 金额: $ 2.43万
• 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: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550119/
• 关键词: Plastic-like phase; alkylurea; alkylthiourea; crystal structure; hydrogen bond; supramolecule; thermal analysis; catenane; チオウレア誘導体; 長鎖アルキル尿素誘導体; 相転移; 三次元超分子集合体; 準プラスチック相; 秩序無秩序転移; 尿素誘導体; rotator Phase; 準柔粘性結晶; プロトンジャンプ

For such compounds as n-butylurea, n-octylurea, symmetric N, N-dibutylurea and dodecylthiourea, plastic-like crystalline phases were found by thermal analyses (DSC). In these cases, the entropy jump of the transition from normal to plastic-like phases amounts to 1/3 1/2 of that of fusion. Single crystal X-ray study elucidated the disorder of alkyl groups in the plastic-like phases and their dynamic nature were studied by solid state NMR methods.Phase transitions were often detected for n-alkylureas. Crystal structure determinations at various temperatures revealed that the mechanism of these transitions was one or two-directional mutual slip of two-dimensional supramolecules constructed by N-H O hydrogen bonds. N-methyl, N-alkylureas with long chain alkyl groups exhibited a common phase transition in the vicinity of melting point. The mechanism of this transition would be similar to that of the n-alkylureas.N-methyl, N-alkylthioureas with long chain alkyl groups exhibited no phase tran … More sitions in contrast to the above cases. This observation could be ascribed to the depression of the thermal motions of the alkyl groups due to a common unique interdigitation of the groups in the crystals.Three-dimensional supramolecular assemblies with distinctive interlocking network via hydrogen bonds were seen in the crystals of 1,5-diureidopentane and 1,4-diureidobutane. DSC experiments on the compounds detected no phase transitions, but established prominent tendency of glass transitions. The crystal structure mentioned above was considered to prevent the phase transitions in the crystalline phase, but to facilitate the formation of considerably stable glassy states.Electric conduction due to proton jump appeared to be possible in butylurea and dodecylthiourea.Characteristics of some physical properties of such compounds as butylurea, octylurea and triptycenequinone could be controlled through modulations of local intermolecular interactions caused by formation of mixed crystal system.Crystal structures and thermal properties were investigated for a lot of urea and thiourea derivatives. Less

对于正丁基脲、正辛基脲、对称 N,N-二丁基脲和十二烷基硫脲等化合物，通过热分析 (DSC) 发现了类塑性晶相。在这些情况下，从正常态到塑性态的转变发生了熵跃。单晶X射线研究阐明了类塑相中烷基的无序性，并研究了它们的动态性质。不同温度下正烷基脲的晶体结构测定经常检测到相变，表明这些相变的机制是由 N-H O 氢键构成的二维超分子的一个或两个方向的相互滑移。具有长链烷基的-甲基，N-烷基脲在熔点附近表现出常见的相变。这种转变的机制与正-烷基脲类似。N-甲基，与上述情况相反，具有长链烷基的 N-烷基硫脲没有表现出相反式位置，这一观察结果可归因于由于晶体中基团的共同独特的叉指而导致的烷基热运动的抑制。在1,5-二脲基戊烷和1,4-二脲基丁烷的晶体中发现了通过氢键具有独特联锁网络的三维超分子组装体。化合物的 DSC 实验未检测到相变，但确定了显着的玻璃化转变趋势。上述晶体结构被认为可以防止结晶相中的相变，但有利于形成相当稳定的玻璃态。由于导电。丁基脲和十二烷基硫脲中的质子跃迁似乎是可能的。丁基脲、辛基脲和三蝶烯醌等化合物的一些物理性质可以通过局部调节来控制。混合晶系的形成引起分子间相互作用。对许多尿素和硫脲衍生物的晶体结构和热性质进行了研究。

项目成果

Exploration of plastic-like phases in alkylurea systems. A thermal and X-ray study

烷基脲体系中类塑料相的探索。

• 发表时间: 2005
• 期刊: J.Mol.Struct. 734
• 作者: M.Hashimoto;F.Tajima;K.Eda;K.Yamamura;T.Okazaki
• 通讯作者: T.Okazaki

Solid solution of triptycenequinone and triptycenehydroquinone as a non-stoichiometric quinhydrone

三蝶烯醌和三蝶烯氢醌的固溶体作为非化学计量醌氢酮

• 发表时间: 2005
• 期刊: Journal of Molecular Structure 737
• 作者: M.Hashimoto;F.Tajima;K.Eda;K.Yamamura;T.Okazaki;Kimiaki Yamamura
• 通讯作者: Kimiaki Yamamura

Three-dimensional supramolecular assembly having infinite two-dimensional interlocking networks built up only from simple and non-rigid organic molecules via hydrogen bonds. Crystal structure of α,ω-diureidoalkanes H_2N(CO)NH-(CH_2)_n-NH(CO)NH_2 with n =

仅由简单且非刚性的有机分子通过氢键构建的具有无限二维联锁网络的三维超分子组装体 H_2N(CO)NH-(CH_2)_n-NH(CO) 的晶体结构。 NH_2 其中 n =

• 发表时间: 2005
• 期刊: J.Mol.Struct. (in press)
• 作者: K.Eda;T.Okazaki;K.Yamamura;M.Hashimoto
• 通讯作者: M.Hashimoto

Three-dimensional supramolecular assembly having infinite two-dimensional interlocking networks built up only from simple and non-rigid organic molecules via hydrogen bonds. Crystal structure of α,ω-diureidoalkanes H_2N(CO)NH-(CH_2)_n-NH(CO)NH_2" with n=4

仅由简单且非刚性的有机分子通过氢键构建的具有无限二维联锁网络的三维超分子组装体 H_2N(CO)NH-(CH_2)_n-NH(CO) 的晶体结构。 NH_2"，n=4

• 发表时间: 2005
• 期刊: J.Molecular Structures 未定(in press)
• 作者: S.Kaneshina;H.Matsuki;M.Kusube;H.Ichimori;Kazuo Eda
• 通讯作者: Kazuo Eda

Solid solution of triptycenequinone and triptycenehydroquinone as a non-stoichiometric quinhydron. Bathochromatic changes in color caused by local intermolecular interaction between p-benzoquinone and hydroquinone moieties

三蝶烯醌和三蝶烯氢醌的固溶体，为非化学计量的醌氢醌。

• 发表时间: 2005
• 期刊: J.Molecular Structures 737
• 作者: Y.Otomo;Y.Nagase;N.Nemoto;Masao Hashimoto;Kimiaki Yamamura
• 通讯作者: Kimiaki Yamamura