Supramolecular Polymers Constructed By Orthogonal Ureidopyrimidinone Quadruple Hydrogen Bonding And Host-Guest Recognition

Supramolecular polymers are aggregate arrays constructed by small molecular weight monomeric units through reversible and highly directional non-covalent interactions. Compared with traditional polymers, they possess distinct new material properties, such as stimuli-responsiveness, self-healing, easy processability due to their dynamic reversible characteristics. Among various non-covalent interactions, the ureidopyrimidinone (UPy) quadruple hydrogen bonding motif was widely used because of its high association constant and synthetic accessibility. Host/guest recognition was also used as it could respond to external stimuli. This thesis consists of three parts based on supramolecular polymers constructed by orthogonal ureidopyrimidinone (UPy) and host/guest recognition motif as follows:1. Supramolecular polymers constructed by orthogonal self-assembly of QHB and benzo-21-crown-7/ secondary ammonium salt recognition.Supramolecular polymers which could respond to external stimuli were constructed based on the orthogonal quadruple hydrogen bonding and crown ether-based host-guest recognition. We designed two kinds of monomers: heteroditopic H1 which contains quadruple hydrogen bonding ureidopyrimidinone (UPy) unit and benzo-21-crown-7 unit, and homoditopic G1 which have two identical dialkylammonium groups. H1 would dimerize through self-assembly of UPy in concentrated solution. The dimer formed by H1 would interact with G1 by host-guest recognition of benzo-21-crown-7/ dialkylammonium to form linear supramolecular polymers. The disassembly-assembly of this supramolecular polymer in solution could be reversibly and orthogonally switched by addition/removal of K+ without interfering of UPy dimerization.2. Supramolecular polymers constructed by naphthalenediimide (NDI) group bridged bifunctional ureidopyrimidinone (UPy) monomers.Our group had researched on the assembly and properties of electron-rich dioxynaphthalene (DNP) group bridged bifunctional UPy molecules with linkers of different lengths. We’d like to study the assembly and properties of electron-poor group bridged bifunctional UPy molecules. So we designed and synthesized naphthalenediimide (NDI) group bridged bifunctional UPy molecule NDI-1. The linker of NDI group and UPy unit is oligo(ethylene oxide) (oligoEO) chain. Due to the π-π stacking interaction of NDI group with dimerized UPy plane, the linear supramolecular polymers constructed by NDI-1 through quadruple hydrogen bonding would futher assemble to form complicated three dimentional architecture which led to the complex of the 1H NMR,13C NMR spectra of NDI-1 in chloroform. While the ’H NMR spectrum of NDI-1 in DMSO is clear because of the destruction of quadruple hydrogen bonding interaction by polar solvent DMSO.3. Research on synthesis and properties of poly(phenylene-ethynylene) (PPE) polymer with pendent pillar[6]arene/pillar[5]arenePoly(phenylene-ethynylene) (PPE) polymer is a kind of fluorescent conjugated polymer. Azobenzene containing compound with long alkyl chain is often used to construct liquid cystal materials. Baed on the fact that azobenzene containing guest can complex with a pillar[6]arene, herein we designed and synthesized poly(phenylene-ethynylene) (PPE) polymer with pendent pillar[6]arene, and study its assembly with long alkyl chain azobenzene compound in cooperation with Professor Chen’group. Moreover, we also designed and synthesized poly(phenylene-ethynylene) (PPE) polymer with pendent pillar[5]arene as reference compound to study its assembly with long alkyl chain azobenzene compound.