Dynamic Imine Macrocyclic Self-assembly Based On Bis-naphthalene And Its Supramolecular Polymer

Different from traditional polymers,supramolecular polymers induce the self-assembly of building units through non-covalent interactions such as hydrogen bonding,host-guest interaction,metal coordination bond and ?-? stacking,to form a new kind of assembly materials with the characteristics of traditional polymers.Due to the dynamic reversibility of non-covalent interactions,supramolecular polymers are different from traditional polymers,with unique properties such as stimulus responsiveness,easy degradation,recyclability,self-repairing ability and so on.In this paper,the dynamic imine macrocycle was constructed by guest template induced bis-naphthalene unit self-assembly.The regularity of ring formation was induced by different guests and different stoppers.And the isomerization selectivity of syn/anti configuration of dynamic imine macrocycles was systematically studied.On this basis,to prepare a novel dynamic imine macrocycle supramolecular polymer by the synergistic self-assembly via multivalent ion guest template induced ring formation and hydrogen bonding.The research content of this paper is divided into the following two parts:1.Different structural guest templates(symmetrical guest,asymmetric guest and spacer group of different sizes)were designed and synthesized.The dynamic covalent self-assembly structures of dialdehyde bis-naphthylene and diamino bis-binaphthylene modules were characterized by NMR.The self-assembly mechanism and macrocycle isomerization regularity of bis-naphthylene modules induced by different structural guest templates were systematically studied.Through the analysis of NMR characteristic peaks of guest templates induced dynamic imine macrocycle self-assembly,the results prove that asymmetric guests induced bis-naphthylene building blocks self-assembly tend to form dynamic imine syn-macrocycle self-assembly structure,while symmetrical guest shows high selectivity to dynamic imine anti-macrocycle.When the volume of the one-side spacer base space increases,the dynamic imine large ring changes to its configuration isomer;when the spacer base space volume is large enough,the object cannot induce the bis-naphthalene motif into a macrocycle.On this basis,the multivalent ion guest template was designed to induce the self-assembly of bis-binaphthylene building blocks to form a complex self-assembly structure with a host guest bonding ratio of 2:1,which laid a foundation for the design and preparation of this type of supramolecular polymers;2.On the basis of the above research work,the supramolecular polymer construction unit is reasonably designed.The bis-naphthylene is used as the host building unit to modify the thymine tail chain and provide hydrogen bonding sites.The multivalent ion guest template induces the bis-naphthylene building unit to form a macrocycle,and the host-guest bonding ratio is 2:1 to form a supramolecular polymer prepolymer.At the same time,a new supramolecular polymer is constructed by using the hydrogen bonding synergy of thymine tail chain.By studying the formation and self-assembly mechanism of supramolecular polymers,it provides new ideas and theoretical basis for the development of new supramolecular polymers.