Self-sorting molecular clips
Self-sorting molecular clips
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DOI：
10.1021/jo8009424
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发表时间：
2008-08-01
影响因子：
3.6
通讯作者：
Isaacs, Lyle
中科院分区：
文献类型：
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作者：
Ghosh, Soumyadip;Wu, Anxin;Isaacs, Lyle
本文报道了12个芳香环上带有氢键基团的C形亚甲基桥连甘脲二聚体（1-12）的合成和表征。化合物1、2、（+/-）-4a、（+/-）-5、（+/-）-7和8在CDCl 3中形成紧密缔合的同二聚体，这是由于π-π和H-键合相互作用的组合驱动力。化合物2、化合物5和化合物8具有不同的氢键基团空间分布，即使在CDCl 3中的三组分混合物中也显示出有效区分自身和非自身的能力。当分子夹的氢键基团的空间分布相似时（例如，1和2），形成同二聚体和异二聚体的混合物。各种结构修饰的效果（例如，手性、侧链空间体积、氢键的数目和模式）对自组装强度和自分选保真度的影响。基于这些结果，我们制备了包括三个（例如，1、（+/-）-5和（+/-）-7）和甚至四个（2、（+/-）-5，9和10）分量。描述了分子夹1-12作为稳健的、可官能化的、自分选的模块来控制系统化学研究中的非共价相互作用网络的潜力。
We report the synthesis and characterization of 12 C-shaped methylene-bridged glycoluril dimers (1-12) bearing H-bonding groups on their aromatic rings. Compounds 1, 2, (+/-)-4a, (+/-)-5, (+/-)-7, and 8 form tightly associated homodimers in CDCl3, due to the combined driving force of pi-pi and H-bonding interactions. Compounds 2, ()-5, and 8, having disparate spatial distribution of their H-bonding groups, display the ability to efficiently distinguish between self and nonself even within three-component mixtures in CDCl3. When the spatial distributions of the H-bonding groups of the molecular clips are similar (e.g., 1 and 2), a mixture of homodimers and heterodimers is formed. The effect of various structural modifications (e.g., chirality, side chain steric bulk, number and pattern of H-bonds) on the strength of self-assembly and the fidelity of self-sorting are presented. On the basis of these results we prepared self-sorting systems comprising three (e.g., 1, (+/-)-5, and (+/-)-7) and even four (2, (+/-)-5, 9, and 10) components. The potential of molecular clips 1-12 as robust, functionalizable, self-sorting modules to control the noncovalent interaction network in systems chemistry studies is described.