Construction And Properties Study Of A New Family Of Functional Supramolecular Metallacycles And Platinum(Ⅱ)-Acetylide Metallogels

Supramolecular chemistry is a chemistry that based on the non-covalent interactions between molecules to form molecular aggregates. With nearly half a century of development, supramolecular chemistry has achieved significant progress. Nowadays, it’s still the main task for supramolecular chemistry to develop new strategies of constructing new structures and explore the applications of their functionality.Recently, the investigation of macrocycle compounds is always one of the most important aspects in supramolecular chemistry. Compared to the "step by step" strategy used to construct macrocycles by traditional covalent bond chemistry, the coordination-driven self-assembly featured significant synthetic advantages such as few steps, quantitative yield, mild conditions, diverse of the final products and so on. When the building blocks used to coordination-driven self-assembly were pre-functionalized, a new family of functional supramolecular metallacycles can be constructed. In addition, platinum(Ⅱ)-acetylene gelators have received widespread attention due to their ease of synthesis and variety of luminescent properties. Firstly based on transition metal platinum(Ⅱ), a series of exo-functional metallacycles have been designed and synthesized in this dissertation. Secondly, platinum(Ⅱ)-acetylene gelators decorated with different functional groups were successfully synthesised and their properties were also studied in the dissertation.The main contents and results are generalized as follows:In Chapter one, we gave a briefly introduction of the concepts of supramolecular chemistry and self-assembly. Then, the development of strategies used to construct different shapes and sizes of functional metallacycles via coordination-driven self-assembly was mainly described. Next, the concept of supramolecular gels was also outlined and the recent developments of platinum containing metallogels were reviewed.In Chapter two, a novel family of ethynylpyrene modified metallacycles have been constructed from newly designed120°ethynylpyrene modified building block via coordination-driven self-assembly. All of these metallacycles were characterized by multinuclear NMR (1H and31P), MS, elemental analysis and PM6molecular model. The studies of their optical spectroscopic behaviors were also carried out, which found that the hexagonal metallacycles constructed from ethynylpyrene modified donor preferred to display excimer emission of the ethynylpyrene groups.In Chapter three, a new family of120°polysulfurated pyridine donors have been successfully designed and synthesized, from which a series of novel polysulfurated metallodendrimers were prepared via coordination-driven self-assembly. Moreover, the preliminary redox properties of these metallodendrimers were also studied.In Chapter four, a discrete hexagonal metallacycle decorated with multiple amide groups and long hydrophobic alkyl chains was constructed via [3+3] coordination-driven self-assembly, from which the regular aggregations and stimuli-responsive supramolecular gels were successfully obtained via hierarchical self-assembly of the discrete hexagonal metallacycles.In Chapter five, a family of new ethynyl-pyrene modified platinum(Ⅱ)-acetylide gelators have been successfully synthesized, which can form stable gels in a variety of solvent mixture through aromatic-aromatic interactions and hydrogen-bonding. Furthermore, the mono-ethynyl-pyrene modified complex could form rigid hybird gels with graphene, which can be applied as a potential media to disperse graphene.In Chapter six, a series of novel platinum(Ⅱ)-acetylide complexes containing tetraphenyl ethylene moieties as the main skeleton have been synthesized and characterized. Their aggregation behaviors in dilute solution and gelation properties in a variety of solvents have been studied. The aggregation induced emission (AIE) behaviors of these platinum compounds were investigated in tetrahydrofuran and water mixture, it is found that tetraphenyl ethylene platinum iodine compounds have presented better AIE properties.In Chapter seven, platinum(Ⅱ)-acetylide complexes decorated with terminal olefin groups have been synthesized. By changing the structure of the platinum(Ⅱ)-acetylide complexes, stable metallogel can be successfully constructed. Furthermore, the olefin metathesis reaction was carried out in the gel phase, after which a more robust metallogel was obtained.In Chapter eight, we gave the conclusions of this dissertation.