| The nature has shown the advantage of supramolecuar chemistry by the formation of DNA double-helixes and the quarternary folding of proteins. Inspired by macromolecules from the nature, supramolecular chemists are expecting to create and develop novel supramolecular systems based on weak noncovalent interactions. Among all of them, rotaxanes have attracted much attention owing to not only their delicate and elegant structures but also their distinct and untouchable properties with the introduction of functional groups. Thus, the development of synthetic methodology of rotaxanes is of great importance. On the other hand, pillararene, as one of the most fantastic supramolecular hosts in the few years, is charming because it is easy to derivate and has the unique host-guest interactions with not only cation guests, for example, ammonium salts, but also neutral ones. The capability to interact with neutral guests makes the pillararene suitable for the construction of rotaxanes with different stoppers. Additionally, platinum-acetylide system has some characteristic photophysical properties with platinum. Moreover, the synthetic procedure of linear neutral platinum-acetylide system is mild and high-yield, and the triethyl phosphine ligands on it have enough large steric hindrance as stoppers. Thus, the introduction of platinum-acetylide moiety gets a double advantage. Construction of organometallic macrocycles via coordination-driven self-assembly is also one of the most fields in supramolecular chemistry. Except for the development of ligands with appropriate angles to satisfy some complex toplogical structures, functionalization is now increasingly important.In this thesis, the construction of metallaorganic supramolecular self-assemblies via Pt-C or Pt-N bond was described and the properties of the self-assemblies were investigated. The main contents and results of this thesis are summarized as follows. In the first part, an overview of construction methodologies and applications of rotaxanes, neutral platinum-acetylide system are introduced. The development of coordination-driven self-assembly has also been reviewed in this part.In the second part, a [2]roatxane platinum-iodide precursor containing pillar[5]arene driven by C-H…π interaction is designed and synthesized. And the following coupling reaction of this [2]rotaxane precursor with acetylide-decorated tetraphenylmethane offered a [5]rotaxane with tetraphenylmethane as core in high yield. The target molecule was confirmed and well-characterized with multi-nuclear NMR spectroscopy and mass spectroscopy.In the third part, based on the mothed developed in the second part, a family of multirotaxanes with tetraphenyl ethylene as core is designed and synthesizd. These rotaxanes were all confirmed and characterized with multi-nuclear NMR spectroscopy, mass spectroscopy and PM6 Semi-empirical molecular orbital simulation. Moreover, these multirotaxanes has a property of aggregation-induced emission enhancement.In the fourth part, a [5]rotaxane with zinc-porphyrin was designed and synthesized. The target molecule was confirmed and characterized with multi-nuclear NMR spectroscopy, mass spectroscopy and PM6 Semi-empirical molecular orbital simulation. The aggregation modes both in solution and on surface were investigated in detail.In the fifth part, two novel ligands with rhodamine derivative and naphthalimide derivative respectively was designed and synthesized. With coordination-driven self-assembly with 120°diplatinum acceptor, two [3+3] assemblies were obtained. Though for the metallocycle with naphthalimide derivative, the fluorescence signal was not stable, the metallocycle with rhodamine derivative showed fluorescence response when pH changed from 4.0 to 6.5, wider than the ligand response pH range from 4.7 to 6.0, which was contributed to the coordination-driven self-assembly strategy. |
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