Novel Rhenium(?) Tricarbonyl Complexes Towards Catalytic, Photophysical And Biological Applications

In the past few decades,rhenium???tricarbonyl complexes have been widely used in various fields due to their unique photophysical and electronic properties.In this thesis,new [Re?N^N??CO?₃X]n+ complexes?N^N is Pyta [2-?1,2,3-triazol-4-yl?pyridine] or Tapy [2?1,2,3-Triazol-1-yl?pyridine]?were designed and synthesized.Their photophysical,electrochemical properties and application as protein-protein interaction inhibitor were investigated.The photophysical properties of the [Re?N^N??CO?₃X]n+ complexes can be regulated by orbital energy levels.In the first chapter,we explored the effects of modification of N^N ligands or axial X ligands on photophysical properties.Firstly,a series of ruthenium complexes were synthesized and characterized by NMR,HRMS and IR spectroscopy.The electrochemical and photophysical properties were systematically studied,and their molecular orbitals were deeply studied through theoretical calculations.In the second chapter,in collaboration with F.Bedioui and M.Fontecave,we explored the structure-activity relationship of ruthenium complex as the catalyst to homogeneously catalyse CO₂ electrochemical reduction.Meanwhile,the catalyst is grafted on the electrode surface in order to achieve heterogeneous catalysis.Two grafting methods were explored: electrochemical immobilization and grafting by noncovalent interactions.Re???complexes functionalised with aniline group or pryene unit were designed and synthesized for this purpose.The modified electrodes were prepared and their catalysis and selectivity for CO₂ electroreduction were preliminarily evaluated.In the last chapter,rhenium complexes were utilised in the design of peptide secondary structures to regulate protein-protein interactions.The introduction of the rhenium complex first stabilizes the secondary structure of the peptide and second provides a fluorescent imaging site.In this part of the work,the Keap1-Nrf2 interaction was chosen as the feasibility study for this strategy.A residue of Nrf2 folds into a ?-turn structure when interacting with Keap1.The Pyta ligand generated by intramolecular Cu AAC reaction closes the macrocycle and provides the reaction site for rhenium complexation.This Ph.D.thesis focuses on the design and synthesis of novel ruthenium???tricarbonyl complexes and their electrochemical and photophysical properties.Based on this,the potential applications in the electrochemical reduction of carbon dioxide and the design of secondary structure of peptides were explored.This work enriches the rhenium???tricarbonyl complexes family.