Design And Synthesis Of Fundamental Assemble Unit And Fluorescence Molecular Clips Based On Diethoxylcarbonyl Glycoluril

In the theory of classical covalent synthesis, the functional group with reaction-activity is the basis of oriented synthesis of complex molecule. With the development of supramolecular chemistry, the non-colvalent synthesis technology is becoming one of the leading research fields in synthetic chemistry. As the basis of those research, the application of noncovalent bonds, such as hydrogen-bond,Ï€-Ï€interaction etc., is actually receiving more and more attention from the public. How to use the covalent molecules of structural diversity to aggregate orientedly and construct the supramolecular materials of advanced-order structure and specific function with those noncovalent bonds becomes the dream that many suprachemists who devote themselves to the field are pursuiting assiduously today.At first the thesis made a relatively comprehensive statement about the application ofÏ€-Ï€interaction in the field of supramolecular chemistry, esp. emphasized upon the progress of theÏ€-Ï€interaction research in the self-assembly system of aromatic supramolecule.Secondly, in view of our previous research foundings upon the noncovalent synthesis (J. Org. Chem., 2006, 71, 4502-4508), we designed and synthesized another type of predictable fundamental assemble modulars in the process of self-assembly, and obtained nine kinds of new asymmetric molecular clips in all based on diethoxycarbonyl glycoluril so as to expand our research concept meantime, i.e. constructing complex molecular stacking thru hierarchical self-assembly. And all structures of the molecules were characterized by IR, MS, ¹H NMR, ¹³C NMR respectively. We also analysized and commented on those complicated nuclear magnetic signals involved in ¹H NMR. However, the pity is we only accomplished the covalent synthesis, but failed to obtain the single crystal construction of the target molecules. As a result, we got no way to fully prove the self-assembly model of the target chemical compound.In addition, more and more people are showing their interests upon the research of supramolecular host in fluorescent chemosensor nowadays. As the molecular clip of glycoluril is also an important supramolecular host and few study had been done in the field of fluorescent chemosensor, we proceeded with some experiments and research in this field as a trial and designed four types of multilocus fluorescent molecular clips. And three of them were synthesized and obtained with diethoxycarbonyl glycoluril as basic building block and bipyridine acetylenylbenzene as fluorophore. We obtained the single crystal structure of III-5a and could be the first one who foundÏ€-Ï€interaction between acetenyl and pyridine ring in the secondary structure of the single crystal. At the same time, we determined the quantum yeilds of the three, and tested 15 metal positive ions to their fluorescence influence, Ag⁺, Cu²⁺, Ni²⁺, Fe³⁺, Al³⁺, Cr³⁺ and Co²⁺ had the quenching effect, in which the sensitivity of Cu²⁺ and Ni²⁺ was good, in particular Ni²⁺.