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建筑和超分子集群与二元或三元铵Triphenylacetates一系列的体制性对称研究

Published: February 15, 2016
doi:

Özet

This article describes construction of a series of hydrogen-bonding supramolecular clusters in crystals using primary ammonium triphenylacetates, which are recrystallized from non-polar solvents. This selective construction of the supramolecular clusters leads to effective systematical symmetric studies about a correlation between the supramolecular clusters and their components.

Abstract

在纳米或亚纳米级集群功能显著取决于不仅种类及其部件,而且安排,或对称,其组成部分。因此,在群集的安排已被精确地表征,特别是对金属配合物。与此相反,在有机分子组成的超分子簇分子安排表征限于少数病例。这是因为,超分子簇,尤其是获得了一系列超分子簇的结构,是困难的,由于非共价键的稳定性低比较共价键。从这个观点出发,有机盐利用是最有用的策略之一。一系列的超分子可以通过与各种抗衡离子的特定有机分子的组合来构造。尤其,伯铵羧酸盐是适合作为超分子因为各种羧酸的典型例子和伯胺是市售的,而且很容易改变其组合。以前,有人证实,使用各种伯胺的伯铵triphenylacetates具体构造超分子簇,这是由四个铵和四个triphenylacetates通过电荷辅助氢键组装时,在从非极性溶剂得到的结晶。这项研究表明超分子集群作为一种战略来进行系统性研究对称澄清在超分子的分子安排和种类及其组件的数量之间的相关性的具体构造的应用。与triphenylacetates构成二进制的盐和一种伯铵的,triphenylacetates组成三元有机盐和两种铵的相同的方式构造的超分子簇,得到与部件的各种种类和数量的一系列超分子簇的。

Introduction

超分子是有趣和重要的研究目标,因为其独特的功能,如建筑超分子结构的,离子和/或分子,以及手性分离的感测,使用柔性非共价键1-11来自它们的分子识别能力。在分子认可,超分子组装的对称性是最重要的因素之一。尽管重要性,但仍然难以与由于在数量和种类的组件以及角度和非共价键的距离灵活性所需的对称性设计超分子。

基于系统化的研究超分子及其部件的对称性之间的相关性的澄清,是实现所需的超分子结构有用的策略。为了这个目的,超分子簇被选定为研究的目标,因为它们是由部件的数量有限的d为评估的理论12-14。然而,与金属配合物,有的构建超分子簇由于非共价键的稳定性低对维持超分子结构15,16的报告的数量有限。这个低稳定性也成为在获得一系列具有同种结构的超分子组装的问题。在这项研究中,有机盐,这是最稳健的非共价键17-20的一个电荷辅助氢键,主要用于构造特定超分子组装优先21-32。它还值得注意的是有机盐是由酸和碱,并且因此许多种有机盐仅仅通过酸和碱的不同组合的混合很容易获得。尤其,有机盐是对系统的研究中是有用,因为与各种抗衡离子的特定成分的组合产生相同类型supramo的lecular组件。因此,能够以比较根据各种抗衡离子的超分子组装的结构上的差异。

在以前的作品,超分子与0维(0-D)中,一维(1-D)和二维(2-D)由伯铵羧酸氢键网络被确认,并从手性的观点来看,其特征32。这些多维超分子是分层的水晶设计27重要的研究目标,以及利用其维度的应用。另外,氢键网络的表征将得到约生物分子的,因为所有的氨基酸的作用的重要知识有铵和羧酸基团。提供指引,以获得这些超分子分别使他们在应用进一步的机会。在这些超分子,建设的超分子簇以0-D-氢键网络是relativelŸ困难,表现在统计研究,28。然而,澄清的因素为构成超分子簇后,将它们有选择地构成,得到21-25,32一系列超分子簇。这些作品使人们有可能在超分子簇进行系统化对称的研究,阐明了超分子簇的依赖分量对称特性。为了这个目的,伯铵triphenylacetates的超分子簇具有有趣的特点,那就是,其拓扑多种氢键网络24,32,这将反映其对称的功能,以及作为组分三苯甲基的手性构象图1a和1b)中 。这里方法论构建一系列使用伯铵triphenylacetates超分子簇和用于表征超分子簇的对称特征是魔trated。对于超分子簇的结构键引入从非极性溶剂的有机盐的笨重三苯甲基的和重结晶。二元和三元伯铵triphenylacetates被用于超分子簇的结构制备。从氢键网络24,32三苯甲基33,34,形貌(构象),和分子安排octacoordinated多面体12(图1c)的类似物拓扑观点考虑晶体学研究揭示了超分子簇的依赖分量对称特性25。

Protocol

1.单晶制备组合主铵Triphenylacetates的制备的有机盐,伯铵triphenylacetates(图1a)。 溶解三苯基乙酸(TPAA,0.10克,0.35毫摩尔)和伯胺:N丁胺(N卜,2.5×10 -2克,0.35毫摩尔),异(isoBu,2.5×10 -2克,0.35毫摩尔),T丁胺(叔卜,2.5×10 -2克,0.35毫摩尔),或在TPAA 吨 -amylamine(叔上午,3.0×10 -2克,0.35毫…

Representative Results

TPAA和伯胺的有机盐形成分别通过FT-IR测量的证实。有机盐的晶体结构经单晶X-射线衍射测定进行分析。其结果是,同种的超分子簇,这是由四个铵和四个triphenylacetates通过电荷辅助氢键(图1a)的,是在所有的有机盐的单晶确认种类和数量而不管成分铵(表1, 图2)。这一结果适用于系统性对称性研究,以澄清相关组件对称品种超分子…

Discussion

一系列封闭的氢键网络的超分子簇的成功构建和使用TPAA,其中有一个三苯甲基,及各类与伯胺的组合的有机盐手性的观点和多面体特征表征。在该方法中,关键的步骤是引入具有从非极性溶剂中的分子和反离子组成的有机盐膨松三苯甲基和重结晶的分子。这是因为,超分子簇具有一个倒胶束结构,即,离子氢键和疏水烃是内,外,分别。因此,该超分子簇是稳定的,在非极性环境中被选择性地构…

Açıklamalar

The authors have nothing to disclose.

Acknowledgements

This work was financially supported by Grant-in-Aid for Scientific Research B (24350072, 25288036) and Grant-in-Aid for Scientific Research on Innovative Areas (24108723) from MEXT and JSPS, Japan. T.S. acknowledges Grant-in-Aid for JSPS Fellows (25763), the GCOE Program of Osaka University and Grants for Excellent Graduate Schools, MEXT, Japan.

Materials

Triphenylacetic acid Aldrich T81205-10G
n-Butylamine TCI B0707
Isobutylamine TCI I0095
tert-Butylamine TCI B0709
tert-Amylamine TCI A1002
Methanol Wako 131-01826 hazardous substance
Toluene Wako 204-01866 hazardous substance
Hexane Wako 085-00416
KBr Wako 165-17111

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Sasaki, T., Ida, Y., Yuge, T., Yamamoto, A., Hisaki, I., Tohnai, N., Miyata, M. Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates. J. Vis. Exp. (108), e53418, doi:10.3791/53418 (2016).

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