Construction of Self-Assembled Unsymmetrical Nanocapsule Space Ditected to Molecular Devices

分子器件定向自组装不对称纳米胶囊空间的构建

• 批准号: 17350067
• 负责人: KOBAYASHI Kenji
• 金额: $ 9.63万
• 依托单位: Shizuoka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-17350067/
• 关键词: Molecular Self-Assembly; Capsule; Unsymmetrical Nano-Space; Supramolecule; Host-Guest; Molecular Recognition; Encapsulation; Control of Orientation; ホスト-ゲスト

We studied on the construction and elucidation of functions of unsymmetrical molecular capsules self-assembled by hydrogen bonds or metal-coordinations. Our findings in this study are as follows.(1) We synthesized bowl-shaped cavitands 1〜7 with hydrogen-bonding sites or metal-coordination sites. We found that 1 and 3, 4 and 5, and 4, 6, and Pd(dppp)(OTf)_2, self-assemble into hydrogen-bonded heterocapsules 1・3 and 4・5, and metal-coordination heterocapsule 4・6・4[Pd(dppp)]^(8+), respectively.(2) We found that these heterocapsules encapsulate unsymmetrical guests with high orientational selectivity what is called "orientational isomerism".(3) The structural and/or electronic environments of one half-capsule unit of the heterocapsule are different from those of the other half-capsule unit. We found that the delicate balance among electrostatic potential repulsion between the lone pair of the carbonyl oxygen atom of a guest and the aromatic cavity of a cavitand, attractive CH-πinteraction, or attractive CH-halogen (halogen-π) interaction in a heterocapsule-guest assembly influences the orientational isomeric selectivity of unsymmetrical guests within heterocapsule.(4) Fine and/or drastic tuning of capsule space has been attained by alteration of the hydrogen-bonding linker and/or hemispherical cavitand, respectively.

本文研究了通过氢键或金属配位自组装的不对称分子胶囊的构建及其功能的阐明。我们在这项研究中的发现如下。(1)我们合成了具有氢键或金属配位的碗状空穴配合物1 ~ 7。我们发现1和3、4和5、4、6和Pd（dppp）（OTf）_2分别自组装成氢键杂胶囊1·3和4·5以及金属配位杂胶囊4·6·4[Pd（dppp）]^（8+）。(2)我们发现，这些杂胶囊封装的不对称客人具有高取向选择性，这就是所谓的“取向异构”。(3)异质胶囊的一个半胶囊单元的结构和/或电子环境不同于另一半胶囊单元的结构和/或电子环境。我们发现在杂胶囊-客体组装体中，客体的羰基氧原子的孤对电子与空穴的芳香空穴之间的静电势排斥、吸引CH-π相互作用或吸引CH-卤素（卤素-π）相互作用之间的微妙平衡影响了杂胶囊内不对称客体的取向异构选择性. (4)胶囊空间的精细和/或剧烈的调整已经分别通过改变氢键连接体和/或半球形空腔来实现。

项目成果

Synthesis and cofacial π-stacked packing arrangement of 6,13-bis(alkylthio)pentacene

• DOI: 10.1021/ol060679x
• 发表时间: 2006-05-25
• 期刊: ORGANIC LETTERS
• 影响因子: 5.2
• 作者: Kobayashi, Kenji;Shimaoka, Reishi;Yamaguchi, Kentaro
• 通讯作者: Yamaguchi, Kentaro

Orientational Isomerism and Binding Ability of Nonsymmetrical Guests Encapsulated in a Self-Assembling Heterodimeric Capsule

自组装异二聚胶囊中非对称客体的方向异构和结合能力

• 发表时间: 2005
• 期刊: Chemistry -A European Journal 11
• 作者: K. Kobavashi,* K. Ishii;M. Yamanaka
• 通讯作者: M. Yamanaka

Interfacial Electronic States of an Anthracene Derivative Deposited on a SiO2/Si Substrate

沉积在 SiO2/Si 基底上的蒽衍生物的界面电子态

• 发表时间: 2006
• 期刊: Solid State Communications 139
• 作者: H. Sasaki;Y. Wakayama;T. Chikyow;M. Imamura;A. Tanaka;K. Kobavashi
• 通讯作者: K. Kobavashi

Tunable Capsule Space : Self-Assembly of Hemispherical Cavitands with Hydrogen-Bonding Linkers

可调胶囊空间：带有氢键连接体的半球形空配体的自组装

• 发表时间: 2006
• 期刊: The Journal of Organic Chemistry 71
• 作者: M. Yamanaka;K. Ishii;Y. Yamada;K. Kobayashi*
• 通讯作者: K. Kobayashi*

Unsymmetrical Nanospace: Self-Assembling Heterodimeric Capsule.

不对称纳米空间：自组装异二聚胶囊。

• 发表时间: 2006
• 作者: K. Kobayashi;他2名
• 通讯作者: 他2名