Lafitte Valérie G H, Aliev Abil E, Horton Peter N, Hursthouse Michael B, Bala Kason, Golding Peter, Hailes Helen C
Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK.
J Am Chem Soc. 2006 May 24;128(20):6544-5. doi: 10.1021/ja0587289.
In view of the range of properties required from supramolecular materials, there is clearly a need for new strong quadruple hydrogen bonded modules, which can be used in polymer or copolymer synthesis via the self- or hetero-association of complimentary units. A cytosine-based module has been prepared for supramolecular applications using a straightforward synthetic approach. The cytosine module was designed such that it does not undergo tautomeric changes observed with ureidopyrimidinones. The cytosine module was capable of forming quadruple hydrogen bonded assemblies both in solution and in the solid state, and the structure of the dimeric self-assembled unit was confirmed by single-crystal X-ray and solution NMR techniques. The dimerization constant was estimated to be greater than 9 x 106 M-1 in deuterated benzene. The capacity of the cytosine-based module to strongly hetero-associate with the ureidopyrimidinone module was demonstrated, and a supramolecular polymer of a bifunctional unit incorporating the cytosine module and PEG-based linker was described.
鉴于超分子材料所需的一系列性能，显然需要新型的强四重氢键模块，这些模块可通过互补单元的自缔合或异缔合用于聚合物或共聚物合成。已使用一种直接的合成方法制备了基于胞嘧啶的模块用于超分子应用。设计胞嘧啶模块时使其不会发生脲基嘧啶酮所观察到的互变异构变化。胞嘧啶模块能够在溶液和固态中形成四重氢键组装体，并且通过单晶X射线和溶液核磁共振技术确定了二聚体自组装单元的结构。在氘代苯中，二聚化常数估计大于9×10⁶ M⁻¹。证明了基于胞嘧啶的模块与脲基嘧啶酮模块强烈异缔合的能力，并描述了一种包含胞嘧啶模块和聚乙二醇基连接体的双功能单元的超分子聚合物。
