Pathway complexity in supramolecular polymerization

摘要: Kinetic control of the self-assembly π-conjugated oligomer S-chiral oligo(p-phenylenevinylene) (SOPV) reveals two competing pathways, leading to a kinetically favoured metastable product and thermodynamically stable with opposite helicity, but addition chiral tartaric acid changes assembly process produce only desired product. Synthetic supramolecular polymers offer range potentially useful properties are finding application in, for instance, organic electronics, as coating materials adhesives. The performance such depend on organization molecular building blocks, which in turn depends pathways involved their self-assembly. Korevaar et al. have taken detailed look at formation uncovered parallel assemblies helicity. One these assemblies, discovered through kinetic analysis, is can be stabilized force aggregation down previously unfavoured pathway. This raises prospect that tuned obtain morphology, thus enabling optimization self-assembled functional materials. Self-assembly provides an attractive route materials, hence depending sensitively blocks1,2,3,4,5. Molecular direct consequence process, more amenable study when using one-dimensional systems. In case protein fibrils, growth been attributed complex pathways6,7,8 go beyond traditional concepts homogeneous9,10,11 secondary12,13,14 nucleation events. synthetic has also studied even modulated15,16,17,18, our quantitative understanding processes remains limited. Here we report time-resolved observations from oligomers. Our experiments show presence forms quickly then transforms into form. Quantitative insight was obtained model calculations, revealed These insights prompt us use auxiliary change thermodynamic preference process19. We find completely pathway so that, removal auxiliary, assemblies.