Synthesis And Property Studies Of Aggregation-induced Light Emission Transition Metal Complexes

In this thesis,six novel diamine compounds of L-1^L-6 were synthesized and used to prepare the corresponding Re???complexes of Re-1^Re-6.Both the diamine ligands and the Re???complexes have the characters of the aggregation-induced emission?AIE?and optical oxygen sensing.In order to clearly understand their photophysical properties,theoretical simulations to the ground-state geometry structures and UV-visible absorption spectra of Re-1^Re-6 were alos performed.The main researching work is as follows:1?Six diamine compounds of L-1^L-6 were designed and synthesized in this thesis and their photophysical properties were fully characterized.The PL spectra of L-1^L-6were measured to be in the range of 420⁵50 nm.At the same time,L-1^L-6 pocess the aggregation-induced light emission character.Electrochemical data show that the dimethylamino groups in L-4 could lead to about 0.31 eV increase of its E_HOMO value compared to those of the other diamine compounds.2?Re???complexes of Re-1^Re-6 were syntheszed by the reactrions of Re?CO?₅Br and L-1^L-6,repectively.In the THF solution,the emission peaks of the complexes Re-1^Re-6 are all between 313⁴15 nm,which are attributed to the???*charge transfer transitions.But the PL spectra of the powders of Re-1^Re-6 locate in the range of 420⁵73 nm,which should be attributed to the MLCT transitions.These data indicate that Re-1^Re-6 should have the AIE character.Electrochemical analysis shows that compared to others,the dimethylamino groups in Re-4 and the organosilane groups in Re-6 lead to the increase of 0.15 eV and 0.28 eV,respectively.The intensity of the PL spectra of Re-1^Re-6 in pure oxygen are about 33.4%,31.7%,28.2%,22.9%,52.3%and 53.6%remained compared to those in the pure nitrogen,respectively,presenting that Re-1^Re-6 could be used as optical oxygen sensing materials.3?The molecular ground state geometries,electronic structures and UV-Vis absorption spectra of the synthesized transition metal complexes Re-1^Re-6 were theoretically simulated at the B3LYP/?LANL2DZ+6-31G?level.The LUMOs of Re-1^Re-5 are mainly composed of?*orbitals of the ligands,while the LUMO of Re-6 is mainly consist of the d*?Re?orbits?*?CO?orbits.The HOMOs of Re-1^Re-3 and Re-5 are mainly composed of d?Re?orbitals and??CO+Br?orbitals.The HOMOs of Re-4 is mainly composed of?orbitals of dimethylamino group,but that of Re-6 is mainly composed of Bath's?orbital.