| Supramolecular chemistry is an important research field in current chemistry. Cyclodextrin and Calixarene derivatives as the first generation and second generation host compounds have been widely applied in the molecular recognition and construction of supramolecular assembly.In this thesis,perylene bisimide-bridged bis-(permethyl-β-cyclodextrins),perylene bisimide-bridged bis-(permethyl-ethylenediamino-β-cyclodextrins), naphthalene diimide and pyromellitimide bridged permethyl-β-cyclodextrin,and a series of calixarene derivatives were synthesized. Furthermore,their assembly behaviors,molecular recognition and photoinduced electron transfer process in the supramolecular assembly were investigated.The major contents of this thesis are as follows:1.The new progress and important achievement of photoinduced electron transfer based on cyclodextrin,the photoinduced electron transfer process between imide derivatives and porphyrin,the self-assembly behavior of perylene bisimides and the fluorescence sensor based on calixarene were described briefly.2.A series of cyclodextrin and calixarene derivatives were synthesized, including:two perylene bisimide-bridged bis-(permethyl-β-cyclodextrins),two naphthalene diimide and pyromellitimide bridged permethyl-β-cyclodextrin,two ferrocence and pyrene modified permethyl-β-cyclodextrins,two calix arene-briged permethyl-β-cyclodextrin and five calixarene derivatives.These structures were proved by NMR,MS,IR and elemental analysis.3.One nanoscopic supramolecular aggregate was constructed from perylene bisimide-bridged bis-(permethyl-β-cyclodextrins) CD-1 viaπ…πstacking interactions.Its self-assembly behaviors in organic and aqueous solutions were investigated by UV-Vis,fluorescence and 1H NMR spectroscopies.The TEM and SEM images show the one-dimensional nanorod aggregation of CD-1,which is birefringent under crossed polarizer conditions,and strongly fluorescent as depicted in the fluorescence microscopy image.X-ray powder diffraction measurement indicates that CD-1 forms a well-ordered crystalline arrangement withπ…πstacking distance of 4.02(?).Furthermore,the solid-state fluorescent sensing was explored by utilizing the poly(vinylidene fluoride) membrane-embedded CD-1,giving that CD-1, as one novel vapor detecting material,can probe several kinds of volatile organic compounds,and especially,exhibits high sensitivity to organic amines.4.Theπ…πstacking behavior of perylene bisimide-bridged bis-(permethyl-ethylenediamino-β-cyclodextrins) (CD-2) was investigated by UV-Vis,fluorescence and 1H NMR spectra,showing that CD-2 exhibited strongπ…πstacking interaction in water.Especially,the aggregation and optical properties were comprehensively compared between the neutral form and protonated form of CD-2 through the concentration-dependent and temperature-dependent UV-Vis experiments.The aggregation constant of CD-2 at the protonated form is almost one order of magnitude lower than that of CD-2 at the neutral form owing to the electrostatic repulsion among CD-2 themselves.On the other hand,CD-2 at the protonated form exhibits better fluorescence than the neutral form by overcoming the photoinduced electron-transfer process from imino groups to perylene backbones.Furtherfore,four water-soluble aromatic guests were used to investigated the complexing interactions with CD-2.Because of the electron interactions between the host and guests and the changes of the aggregation behavior induced by the complex of the guests,the absorbance of CD-2 was obvious red shift,which displaied sensing for 2-anthracene acid sodium and pyrene-butyl acid sodium.5.A series of supramolecular wirelike assemblies were constructed by the naphthalene diimide and pyromellitimide bridged permethyl-β-cyclodextrins upon complexation with water-soluble(metal) porphyrins,which were comprehensively characterized by UV-Vis spectroscopy,NMR,atomic force microscopy,scanning electron microscopy,and gel permeation chromatography.Fluorescence and electrochemical measurements demonstrated that the effective electron-transfer processes were observed in the regular arrays of multiple donors and acceptors formed by naphthalene diimide bridged permethyl-β-cyclodextrin and porphyrins, while did not for the case of pyromellitimide bridged permethyl-β-cyclodextrin. Moreover,the electron-transfer efficiencies mainly rely on the distinguishable excited energies of porphyrin and metal porphyrin.And the possible reasons were investigated by electrochemistry analysis,reorganization energy analysis and circular dichroism spectrum.6.Supramolecular complex was constructed by perylene bisimide-bridged bis-(permethyl-β-cyclodextrins) CD-1 upon complexation with water-soluble porphyrin,which were comprehensively characterized by UV-Vis spectroscopy.The photophysical hebavior of the supramolecular complex was investigated by fluorescence spectrum and fluorescence lifetime.The observed behavior sharply changes with excitation wavelength,depending on whether the porphyrin or the perylene bisimides units are excitation.After porphyrin excitation,the fluorescence typical of this unit is quenched about 80%,because of the photoinduced electron transfer from porphyrin to perylene bisimides.Upon excitation of the perylene bisimides fragment,the fluorescence was quenched due to the energy transfer process from perylene bisimides to porphyrin.And the strong exciton coupling interactions between perylene bisimides and porphyrin were studied by UV-Vis and circular dichroism spectrum.7.The chemosensing behaviors of host compound for alkali and alkaline earth metal ions were investigated by fluorescence spectroscopy.The obtained results show that the calixarene host can selectively bind sodium ion with the complexation stability constant of 2190 mol-1·L.The complexation with sodium ion can pronouncedly induce the excimer emission decreased and the monomer emission increased,whereas the addition of the other alkali and alkaline earth metal ions does not cause appreciable changes in the fluorescence spectrum of the host compound.
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