| Molecular machines, as one of the most challenging topic in the field of supramolecular chemistry, have attracted continuing interest and attention. A variety of appealing examples in this field have been fabricated over the recent years, with applications in many areas. Component of the artificial molecular machines could also have relative movement under external specific stimuli as the macro machines, and the movement can be detected. The output signals of most molecular machines were observed by NMR, cyclic voltammetry, circular dichroism, and UV-vis absorption or fluorescence emission. Phosphorescence, especially the room temperature phosphorescence (RTP), is another excellent method expected to be used in this field. RTP can not merely respond quickly and be detected with low cost, but has more advantages, such as longer emission wavelengths and lifetimes, larger Stokes’shifts, higher signal-to-noise ratios, easily measurable lifetimes, etc.In this dissertation, we designed and constructed some pH-controlled bisable molecular shuttles with room temperature phosphorescence on the base of the metalloporphyrin. On the other hand, we constructed a INHIBIT logic gate with room temperature phosphorescence output making use of the Cyclodextrin induced room temperature phosphorescence (CD-RTP). Thus it provides a new means for detecting and identifying molecular machines and for the construction of complicated multi-mode molecular machines. A brief summary is given as follows:Chapter I:We mainly expound the research progress of molecular machine in recent years. The definition and three species of molecular machine, namely rotaxane, pseudorotaxane, and catenane were elaborated. Driving forces of switchable molecular machine, like chemical energy, electrochemical energy, light energy, and others, were exemplified. The identifications of movement of molecular machine, like NMR spectra, ultraviolet-visible absorption spectroscopy, fluorescence spectroscopy, cyclic voltammetry, circular dichroism spectra were introduced, and room temperature phosphorescence spectroscopy as a new method was specially stated. In addition, the potential application of molecular machine in such areas as molecular logic gate, molecular nanovalve, supramolecular polymer and organic gel were also illustrated.Chapter Ⅱ:We designed and synthesized a series of novel24-crown-8ether connected with free-base or metal complexed porphyrin moiety covalently by template method, and characterized by standard spectroscopic methods. The association constant between the host and the guest was determined by fluorescence titration experiment.Chapter Ⅲ:We designed and synthesized a series of novel pH-controlled distable molecular shuttles R1-R3, comprised of metalloporphyrin-based dibenzo[24]crown-8macroring and anthracene unit as one stopper by click chemistry, and the motion of R3could be read out by RTP signals.Chapter Ⅳ:We prepared a light-driven [1]Pseudorotaxane based on the self-inclusion complexation of an azobenzene-modified β-CD, and its photoisomerization and their complexation behaviors with a-bromonaphthalene were adressesed by ICD and room temperature phosphorescence. The INHIBIT logic gates were fabricated conveniently in aqueous solution, utilizing RTP or ICD as outuput.Chapter Ⅴ:We synthesized two compounds which contains tetrapyridylporphyrin core connected with naphthalene or bromonaphthalene and obtained their supramolecular polymer based on the host-guest interaction between CB[7]/CB[8]. We characterized spiropyran coated gold nano rods (GNR) and gold nano particles (GNP) by ultraviolet absorption spectra, fluorescence emission spectrum, IR spetra and Raman spectra. The photochromic properties of spiropyran can affect the plasmon peaks of GNRs but not GNPs.Chapter Ⅵ:A summary of the contents of the entire dissertation... |
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