Rational Design of Multicomponent Calix[4]arenes and Control of Their Alignment in the Solid State
Rational Design of Multicomponent Calix[4]arenes and Control of Their Alignment in the Solid State
复制标题
多组分杯[4]芳烃的合理设计及其固态排列控制
DOI：
10.1021/ja970758r
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发表时间：
1997
期刊：
影响因子：
--
通讯作者：
J. Atwood
中科院分区：
文献类型：
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作者：
L. MacGillivray;J. Atwood
超分子复合体设计的一个主要推动力是对自然界中发现的那些大型、多组分、自组装过程的结构和功能的模仿。1在这样的背景下，主-客体化学领域提供了许多涉及非共价相互作用(例如，氢键、π-π相互作用)的双组分分子识别过程的例子。2然而，这种方法通常涉及单分子主机3，这些主机通常是通过精心设计的共价键的形成和断裂来设计的。2考虑到这一点，我们开始了一项旨在设计由非共价力连接在一起的多组分主体的研究计划。作为起点，我们选择了容易获得的C-甲基杯[4]间苯二酚4(1)作为组装过程的平台。事实上，固态研究揭示了1有能力采用碗状构象，其中四个上缘羟基氢原子向上指向其空腔上方，5这有效地使1成为多个氢键供体。使用最近用于晶体工程的一(1D)和二维(2D)间苯二酚晶格3，6的设计策略，7我们推论，1与氢键受体如吡啶2的共晶将导致1的上缘和4个吡啶单元8之间形成4个OH，N氢键，这反过来将扩展19的空穴，并产生能够捕获大客体1.4(2)客体的多组分主体1.4(2)。在这篇文章中，我们报道了第一批多组份杯芳烃的合成和X射线结构测定。我们证明了吡啶(2a)及其外双齿类似物4，4‘-联吡啶(2b)通过形成能够使1形成包合物的壁来阐述1的空腔的能力
A major impetus for the design of supramolecular complexes is structural and functional mimicry of those large, multicom-ponent, self-assembling processes found in Nature. 1 In such a context, the area of host-guest chemistry has offered numerous examples of two-component molecular recognition processes involving noncovalent interactions (e. g., hydrogen bonds, π-π interactions). 2 Such an approach, however, often involves monomolecular hosts3 which are typically designed Via the elaborate formation and breakage of covalent bonds. 2 With this in mind, we have embarked upon a program of study aimed at the design of multicomponent hosts held together by noncovalent forces. As a starting point, we have chosen the readily available C-methylcalix [4] resorcinarene4 (1) as a platform for the assembly process. Indeed, solid state studies have revealed the ability of 1 to adopt a bowl-like conformation in which four of its upper rim hydroxyl hydrogen atoms are pointed upward, above its cavity, 5 which effectively makes 1 a multiple hydrogen bond donor. Using a design strategy recently employed for the crystal engineering3, 6 of one-(1D) and twodimensional (2D) resorcinol-based lattices, 7 we reasoned that co-crystallization of 1 with hydrogen bond acceptors such as pyridines 2 would result in the formation of four OH ‚‚‚N hydrogen bonds between the upper rim of 1 and four pyridine units8 which would, in turn, extend the cavity of 19 and give rise to a multicomponent host 1.4 (2) capable of entrapping large guests 1.4 (2)‚guest. 10In this contribution we report the syntheses and X-ray structure determinations of the first examples of multicomponent calixarenes. We demonstrate the ability of pyridine (2a) and its exo-bidentate analog 4, 4′-bipyridine (2b) to elaborate the cavity of 1 by forming walls which enable 1 to form inclusion