The Synthesis Of N-substituted Corannulene Derivatives And Its Coordination Assembly

Supramolecular Cages(SCs)are discrete coordination self-assemblies having cage-like well-defined structures and confined cavities.These macromolecules have nano-scale cavities that allow entry,binding,and passage of the guest molecular;at the same time,the special shape and internal en-vironment will let them become an excellent molecular reactor.Therefore,the study of the chemical properties and assembly behavior of supramolecular cages has become the basis for the further application of supramolecular cages.The highly directional and predictable nature of the metalligand coordination sphere is a critical feature of coordination-driven selfassembly.The energies of metal-ligand bonds(15-50 kcal/mol),which are intermediate between the energies of organic covalent bonds(ca.60-120 kcal/mol)and the weak interactions(ca.0.5-10 kcal/mol)that nature employed.By introducing rigidity and reversibility,it provides structural flexibility while constructing large cavity supramolecular cages.Corannulene is a conjugated aromatic hydrocarbon with a bowl-like structure.By introducing the coordination functional group,corannulene will be a potential candinate to construc the supramolecular cage with large curved cavities.Also the C,symmetry will make the supramolecular cages become an interesting construction.The work of this thesis includes the following three parts:1.Synthesis of corannulene and its chlorinated synthon.'The synthesis mainly refered to the existing method,and some experimental steps have been optimized.A sufficient amount of corannulene and its chlorinated synthons were successfully prepared,which laid the foundation for the derivatization.2.The syrnthesis of pyrazolyl-substituted corannulene derivatives and its coordination assembly.The decapyrazolylcorannulene and pentapyrazolylcorannulene are prepared by nucleophilic substitution reaction from the chlorinated corannulene.The structure is characterized by mass spectrometry,nuclear magnetic resonance spectrometer and single crystal X-ray diffraction.The properties were explored by UV-visible absorption spectroscopy,fluorescence spectroscopy and nuclear magnetic titration.The self-assembled with transition metal centers was carried out using decapyrrazolylcorannulene and pentapyrrazolycorannulene as ligand units.The coordination behavior was explored by single crystal X-ray diffraction analysis and nuclear magnetic titration analysis.In the exploration of the coordination self-assembly behavior of decapyrazolylcorannulene and AgCF3SO3,we successfully obtained two different configurations of supramolecular cages;which exhibited unexpected results in the selectivity of stable conformation.The analysis of single crystal X-ray diffraction has discussed their conformational selectivity.Also,The nuclear magnetic titration experiments confirmed the behavior of coordination self-assembly.3,A series of nitrogen-contained corannulene derivatives were prepared by nucleophilic substitution reaction with the decachlorocorannulene.The chemical stability of N-doped corannulene derivatives was explored by comparing their structure and properties.The understanding and explanation to the influence of the electron-withdrawing group,the conjugate system change and the steric hindrance on the reactivity and product stability during the nucleophilic reaction are realized,which will be of great significance for further It provides a great reference for the structural design and selection of our next exploration.