新型刚性酰胺键联双卟啉锌在手性识别中的应用-无机化学专业论文.docx

新型刚性酰胺键联双卟啉锌在手性识别中的应用英文摘要Applications of Novel Rigid Amide-linked Zinc(II) Bisporphyrinates in Chiral RecognitionAbstractChiral recognition is one kind of important molecular recognition in supramolecular chemistry. We have designed and synthesized a series of rigid amide-linked zinc(II) bisporphyrinates. Using them as hosts, we have studied their chiral recognition abilities for chiral guests by circular dichroism spectra, X-ray crystallography, UV-Vis titration, 1H NMR and DFT/TDDFT. The corresponding mechanism has also been probed.In this thesis, we have designed and synthesized four bisporphyrinates containing double amide groups on the basis of mono o-aminophenyl substituted porphyrin, N,N′-Bis[5-(o-phenyl)-10,15,20-triphenylporphyrinato-yl)]oxalic amide zinc(II) (compound 2), N,N′-Bis[5-(o-phenyl)-10,15,20-triphenylporphyrinato-yl)] p-phthalic amide zinc(II) (compound 3), N,N′-Bis[5-(o-phenyl)-10,15,20-triphenylporphyrinato-yl)] m-phthalic amide zinc(II) (compound 4) and N,N′-Bis[5-(o-phenyl)-10,15,20-triphenylporphyrinato-yl)] o-phthalic amide zinc(II) (compound 5). We have studied their chiral recognition abilities for D/L- alanine ethyl ester, D/L- vlaine ethyl ester, D/L- leucine ethyl ester, D/L- phenylalanine ethyl ester, D/L- phenylglycine ethyl ester. Compound 2, 3 and 4 have exhibited strong chiral recognition abilities for amino acid esters.Using compound 2 as a host, we have studied its chiral recognition ability for five amino acid esters. The ICD spectra showed the positive exciton chirality for L-amino acid esters and negative exciton chirality for D-amino acid esters in Soret band. Using 5-(2-(methyl-N-oxamate)-phenyl)-10,15,20-triphenyl-porphyrin Zinc(II) (compo--und 1) and tetraphenylporphyrin Zinc(II) ([Zn(TPP)]） as reference compounds, wehave studied the role of hydrogen bonds in the chiral recognition process by the UV-Vis titration. We have further investigated the hydrogen bonding interactions between the porphyrin host and