Martínez-Crespo Luis, Whitehead George F S, Vitórica-Yrezábal Iñigo J, Webb Simon J
Department of Chemistry, University of Manchester Oxford Road Manchester M13 9PL UK
Manchester Institute of Biotechnology, University of Manchester 131 Princess St Manchester M1 7DN UK.
Chem Sci. 2024 Sep 19;15(41):17120-7. doi: 10.1039/d4sc04337e.
The structural, self-assembly and binding properties of oligo-(phenylene-ethynylene) (OPE) rigid rods linked to squaramides (SQs) have been studied and correlated with rod length. In the solid-state, OPE-SQ conjugates form indefinite arrays of head-to-tail hydrogen bonded SQs, arrays that include both intra- and intermolecular hydrogen bonds. In dichloromethane solution, intramolecularly hydrogen bonded SQ chains show cooperative polarisation, an effect that increases with OPE-SQ length. Appending powerful hydrogen bonding groups to the OPE-SQ termini further increases this intramolecular polarisation. Greater end-to-end polarisation leads to stronger intermolecular interactions, with longer OPE-SQs showing stronger hydrogen bonding to DMSO as well as stronger self-association. These studies show how cooperative hydrogen bond polarisation in a hydrogen bonded array can be strengthened and how this polarisation can continue intermolecularly.
已对连接有方酰胺（SQs）的低聚亚苯基乙炔（OPE）刚性棒的结构、自组装和结合特性进行了研究，并将其与棒的长度相关联。在固态下，OPE-SQ共轭物形成头对头氢键连接的SQs的无限阵列，这些阵列包括分子内和分子间氢键。在二氯甲烷溶液中，分子内氢键连接的SQ链表现出协同极化，这种效应随着OPE-SQ长度的增加而增强。在OPE-SQ末端附加强大的氢键基团进一步增强了这种分子内极化。更大的端到端极化导致更强的分子间相互作用，更长的OPE-SQs对DMSO表现出更强的氢键作用以及更强的自缔合作用。这些研究表明了氢键阵列中的协同氢键极化如何能够得到加强以及这种极化如何能够在分子间持续。
