Research Of Construction And Properties Of Platinum (â…¡) Metal-supramolecular Polymers

Supramolecular polymers are representative of unique and functional supramolecular assemblies together via non-covalent interactions. Not only have favourably photoelectric and reversible characteristics, they also display some response to external environmental stimulating. In recent years, people have been paying attention to the potential value of metal-supramolecular polymers. Constructed by that the transition metal elements of subgroup are transited from mineral resources chemistry to supramolecular chemistry, metal-supramolecular polymers have not only high strength, but also have good photoelectric properties, such as solar cells,fluorescent materials, organic conductive materials and so on. And some subgroup precious metal elements(such as palladium, platinum) confer functional catalyst of supramolecular polymers. Therefore, in terms of construction and research of metal-supramolecular polymers, it not only opens up new areas of mineral resources chemistry, but also provides a significant way for functional supramolecular polymers of mineral resources chemistry.In this dissertation, based on the intermolecular hydrogen bonds, host-guest interactions and aromatic donor-acceptor interactions, platinum(II)metal-supramolecular polymers were designed that they have new and ordered structure through the "bottom to up" self-assembly strategy. It comprises three parts:In the first part, the well-defined supramolecular polymers were based on hydrogen bonding and host-guest interactions through the "orthogonal" self-assembly strategy. Specifically, due to Hamilton receptors/cyanuric acid and benzo-21-crown-7/secondary ammonium salt being combined through hydrogen bonding and host-guest interaction respectively, so Hamilton receptors and cyanuric acid were attached on ends of benzo-21-crown-7 to construct the two homoditopic monomers respectively. Then Mixture of the two monomers could associate with secondary ammonium salt to form the hyperbranched and linear supramolecular polymers. Furthermore, based on1 H NMR, DOSY, and viscosity measurements, it is evident that hyperbranched polymers exhibit more superior and stimuli-responsive properties, and demonstrate significant chain topological-dependent supramolecularpolymerization behaviours, which provides some reference for the third part of whether platinum(II) metal-supramolecular polymers can form different topologies gel.In the second part, the platinum(II) metal-supramolecular polymers were based on hydrogen bonding and donor-acceptor interactions through the “tweezering directed self-assembly” strategy in micromolecule systems. Specifically, the poor-electron molecular having the structur of tweezer was formed by platinum(II)and terpyridine ligands, and it could self-assembly together with a poor-electron polycyclic aromatic molecule pyrene to be the formation of metal-supramolecular polymers having a high degrees of polymerization and spectral properties through hydrogen bonding and donor-acceptor interaction. Furthermore, based on1 H NMR,DOSY, ITC, UV absorption spectros, and viscosity measurements, the degrees of polymerization, spectroscopic properties and thermodynamic behavior have been explored systematically. At the same time the controlled self-assembly and disassembly processes of supramolecular polymers have been achieved by controlling the temperature and chain terminator.On the basis of the second part, in the third part, the above system was transited from micromolecule to macromolecules systems by "valvate oriented" self-assembly strategy, thereby constructed the metal-supramolecular gels with a cross-linked network structure. Specifically, the poor-electron polycyclic aromatic molecule pyrene was attached on ends of polycaprolactone(pcl), and it could form platinum(II)metal-supramolecular polymers having a cross-linked network structure with the above-mentioned valvate system through donor-acceptor interaction. Because of good gelling properties of pcl, so the polymers could easily form a platinum(II)metal-supramolecular gels. Furthermore, based on1 H NMR, UV absorption spectros,viscosity, and DSC measurements, physical and chemical properties of the metal-supramolecular gels will been explored to exhibit favourable rheology and environmental responsiveness.