Synthesis, Characterization, And Properties Of Rhenium(Ⅰ) Complexes With Phenanthroline Ligand

Phenanthroline is a six membered heterocyclic molecule, which has high conjugation extent and ability to accept π electronic to form stable coordination compounds with many metal ions. It is a planar rigid bidentate ligand and has found applications in optical devices, such as fluorescence and magnetic materials.In this paper, we used phenanthroline and its derivatives as ligand to form coordination compounds with rhenium and study the photophysical properties, composition and the structure of the as-obtained coordination compounds.Main works are as follows:1. We designed the ligand:three Re(I) complexes of PNPh-Re,PNPhC2-Re and PNPhC4-Re were synthesized, and the block copolymer of PS-b-PMAA(PNPh-Re),PS-b-PMAA(PNPhC2-Re) and PS-b-PMAA(PNPhC4-Re) which containing Re(I) metal ion was synthesized. Their structures were identified by NMR, IR, MS and so on.2. The coordination complex PNPh-Re displays no emission of3MLCT state in acetonitrile solution. However, the PNPhC2-Re and PNPhC4-Re shown obvious emission, and occurred a blue-shift in the membrane state when compared with the emission peak in the acetonitrile solution.By studying the molecular structure, this is because of the configuration of PNPh changes between the ground state and excited state.3. Density functional theory (DFT) was used to optimize the ground state and excited state structures of the complexes PNPh.PNPhC2and PNPhC4using the MPW1B95/6-31G*basis set. The absorption spectra were calculated using time dependent DFT (TD-DFT) with the same basis set.4. These three different block polymers PS-b-PMAA (PNPh-Re) have the photophysical properties of transition metal complexes of rhenium. And their morphology of self-assembled in the gas-liquid interfacial was investigated in detail. PS188-b-PMAA4(PNPh-Re)180sample has many spheroidal aggregate structure. This structure mainly caused by the large percentage of hydrophobic PS chain segments concentrated on the water surface. The spheroidal aggregate structure decreased along with the PS chain segments percentage reduces.