Study On The Supramolecular Chemical Performance In Water Solution

Crownether, cyclodextrin, calixarene and cucurbituri are four macrocyclic compounds of supramolcular chemistry. Cucurbituril is a hexameric macrocyclic compound self-assembled from an acidcatalyzed condensation reaction of glycoluril and formaldehyde, it has the common character of hydrophobic cavity and two portals of polarity carbonylic oxygen atoms. Cucurbit[n]uril has an exceptional capacity to encapsulate other molecules or ions within its cavity. In the past decade host-guest molecular recognition and assembly has become the central research field in supramolecular chemistry. In this article, Cucurbit[7]uril was been chosen as the host which have best solubility in aqueous solution between cucurbiturils. And we synthesized three calix[4]resorcinarene sulfonic acid derivatives as the hosts. Besides, we synthesized six long-chain hexanediamine hydrochlorides (1a~1f) and five short-chain diaminopropane hydrochlorides (3a~3e) as the guests. A series of significant results and developments have been achieved and the main interesting results are as follows:1. Synthesized cucurbit[n]uril (n=5~8) host compound according to the literature method. Complexation of cucurbit[n]uril and benzidine in the acidic aqueous solution has been studied by using UV spectrum. The recognition effect of the hollow size of cucurbituril for benzidine has been compared, in which CB[7] showed stronger complexation for benzidine, with the depression of the UV absorption of benzidine remarkably. The effect of other cucurbituril is weak. CB[7] is the best choice to recognize benzidine. Complexation of CB[7] with benzidine is investigated thoroughly in the solution system of 0.2mol/L NaCl and 0.1mol/L HCl. According to the experimental results, complexation of CB[7] with benzidine is quite stable. UV spectrum and 1H NMR technique were determined the association constant of CB[7] for benzidine and host-guest complexes'structure characteristic, the ratio of host to guest in complexes, the reaction mechanism and so on.2. Then six linear aromaticring diamidogen guests (1a~1f)were synthesized by reducing Schiff bases of 4-chlor-benzaldehyde, 3-nitro-benzaldehyde, 4-nitro-benzaldehyde, N,N-dimethylaminobenzaldehyde, 4-hydroxy-benzaldehyde, 4-hydroxyl-3-methoxy-benzaldehyde and 1,6-diaminohexane. The five short-chain diaminopropane hydrochlorides (3a~3e) was synthesized by 4-chlor-benzaldehyde, 3-nitro-benzaldehyde, 4-nitro-benzaldehyde, N,N-dimethylaminobenzaldehyde, 4-hydroxy-benzaldehyde and 1,3-propane diamine. The ultraviolet absorption spectrum, the infrared spectrum and the 1H NMR were used to characterized and investigated the interaction between host and guests, such as the interacted condition, the function pattern, as well as the reaction mechanism. Discussed these host-guest complexes'structure characteristic, the ratio of host to guest in complexes, the equilibrium constants and so on.3. Tetramethyl, tetraethyl, and tetraphenyl calix[4]resorcinarenes are alkylated with different alkylation reagents to give three functional sulfonic acid derivatives (MeC, EtC, PhC). We investigated host-guest complexes'structure characteristic, the ratio of host to guest in complexes, the equilibrium constants and so on by using the ultraviolet absorption spectrum technique.