Research And Application Of Chiral Aggregation-induced Emission Molecules Based On Binaphthyl

Recently, as the huge potential in application, chiral materials have achieved increasing attention in the fields of asymmetric synthesis, chiral recognition and resolution, chiral induction and chiroptical materials. 1,1’-binaphthol (BINOL), as a typical axial chiral compound, has been fully used in these areas and obtained great success, which could be ascribed to its strong and stable chirality signal. In addition, its nature of a luminophore endows it better chemical modification. Aggregation-induced emission Luminogens (AIEgens) have got proud achievements in the areas of optical and biological, however, it has been rarely used in the field of chirality. We hold that it will have potential application in the field of chirality, which is based on its RIR mechanism. In this thesis, we have carried out a series of experiments on the synthesis and application of chiral AIEgens.Firstly, we have combined BINOL and tetraphenylethylene (TPE) in different types, and synthesized three compounds of (R)-6,6’-BTPE-BINA、(S)-6,6’-BTPE-BINA and (R)-3,3’-BTPE-BINA. They are all AIEgens and chirality-active, and the chirality more easily transfer from the 3,3’-position of BONOL to TPE. At the same, we have discovered a novel phenomenon of aggregation-annhilation circular dichroism (AACD) in these compounds, further research suggested that it was caused by the change of twist angle between two naphthalene rings during the process of aggregation.Secondly, on the basis of previous work, polymers of P-1, P-2 and P-3 have been designed and synthesized. Signals of circular dichroism (CD) and circularly polarized luminescence (CPL) could be detected in the solid state to polymers P-2 and P-3, but P-1 was inactive. Results of scanning electron microscope showed that P-3 was easy to form spiral microstructures in the aggregation state. We also detected the phenomenon of AACD in polymers P-1 and P-3, but the CD signals of P-2 haven’t changed so much with the increasing of water fraction.Finally, we have designed and synthesized the macrocycle compound of BINOL-Crown-TPE, which was intended to be used in the chiral recognition. The results showed that it was AlEgen, and had advantages on the research of chiral recognition mechanism. But results of the initial attempts were not very satisfactory, which was ascribed to its propeller-like molecular structure. If we want to accomplish the chiral recognition, maybe some decoration will be need on the TPE.