| Chirality is the basic feature life. Organic molecules that composed of life aremost chiral molecules. The researches in this field are among the most important andactive in the past several decades. In 2001, William Knowles (USA), Ryoji Noyori(Japan) and Barry Sharpless (USA) won the the Nobel Prize in chemistry for"pioneering contributions to the field of asymmetric synthesis,"including thediscovery of chiral catalysts for hydrogenation and oxidation.There are different biological activities in enantiomorphs of chiral molecules,which are especially important in the field of pharmaceutical chemistry.Pharmaceutical products often consist of chiral molecules, and the differencebetween the two enantiomeric forms of compounds can be a matter of life and death–as was the case, for example, in the thalidomide disaster in the 1960s. That is whyit is vital to be able to produce the two chiral forms separately. The chirality is of theultimate importance in the fields of life sciences, pharmaceutical chemistry,host-guest chemistry and materials chemistry. Now there are many methods toobtain single enantiomers, including natural compounds, synthesized compoundsbased on natural compounds, asymmetric synthesis and chiral separation.Comparing these methods, the first and second methods are dependent on theavailability of the natural sources. The latter two methods are commonly used andextensively studied. In particular, we consider that chiral separation is the bestchoice for gaining single enantiomers. First, the chiral separation could yield bothenantiomers including the desired enantiomer. Secondly, asymmetric synthesis isvery time-consuming and labor intensive. Chiral recognition is widely recognized asan important research field for chiral separation. The mechanistic aspect of chiralrecognition is also particularly interesting in terms of fundamental science. The aimof this thesis is to design and synthesize chiral poly (aryl ether ketone) (PAEK)cyclic oligomers and polymers containing binaphthyl moieties, and to investigatetheir properties of chiral recognition and the control of the selectivity of chiralrecognition.(1) Synthesis of chiral PAEK cyclic oligomers and polymers containing binaphthyl moieties Initially, the pseudo-high-dilution technique that we employed was a one-stepreaction. However, we found that the product was a mixture, including dualistic ring,ternary ring and multiple rings. It was very difficult to purify the product. Thereforewe modified the initial pseudo-high-dilution technique, and developed a two-stepreaction to synthesize the target macrocycle. The first step was the synthesis ofchiral macromonomer. The second step was the reaction of chiral macromonomerand bisphenol monomer. This method resulted in a significant increase in the yieldof the product. Through modified pseudo-high-dilution, we successfully synthesizedchiral PAEK cyclic oligomers containing binaphthyl moieties. The structures ofthose new compounds were confirmed by IR, NMR and MALDI-TOF-MS, etc.Through a classic aromatic nucleophilic substitution, we succeeded in synthesizing achiral PAEK polymer containing binaphthyl moieties, and characterized its structureby menas of IR, NMR and GPC, etc.(2) Characterization of chiral PAEK cyclic oligomers and polymers containing binaphthyl moieties by vibrational circular dichroism (VCD) technique We characterized the chiral PAEK cyclic oligomers and polymers containingbinaphthyl moieties by VCD technique. We found that the chirality of PAEK cyclicoligomers and polymers containing binaphthyl moieties is originated, as anticipated,from the chiral binaphthyl moieties. The changes in stereochemistry uponincorporation of the binaphthyl groups into the chiral macromonomer, chiral cyclicoligomers and chiral polymers were observed in their VCD spectra. Based oncomputer simulations and VCD data, we determined the structure of two types ofchiral cyclic oligomers, including bond lengths, bond angles and dihedral angles.(3) Chiral recognition based on chiral PAEK cyclic oligomers and polymers containing binaphthyl moieties The results from DSC, IR and UV-Vis studies indicate that the chiral polymercould recognize chiral binaphthol. The driving forces of chiral recognition are theformation of hydrogen bond between the carbonyl group in the chiral polymer andthe hydroxyl group in the chiral binaphthol and the π-π* interactions between thephenyl and binaphthyl groups. Based on the results from electrochemicalexperiments, we found that the chiral cyclic oligomer could recognize chiral...
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