Browsing by Author "Huang, Feihe"
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- Host-Guest Systems Based on Crown Ether, Cryptand, and Pseudocryptand Hosts with Paraquat, Diquat, Secondary Ammonium, and Monopyridinium Salt GuestsHuang, Feihe (Virginia Tech, 2005-03-16)Supramolecular host-guest chemistry is a topic of great current interest. However, the further development of host-guest chemistry is still limited by the number of available host-guest recognition motifs. This makes it necessary and valuable to find new host-guest recognition motifs and apply known host-guest recognition motifs in the preparation of novel supramolecular systems. By comparing the crystal structures of the host and its taco complex, we proved that folding is a necessary step during the formation of taco complexes. Based on the known bis(m-phenylene)-32-crown-10/paraquat recognition motif, the first solid-state supramolecular poly(taco complex) was prepared. We demonstrate not only that bis(m-phenylene)-32-crown-10-based cryptands are powerful hosts for paraquat derivatives compared with the simple crown ether, but also that cooperative complexation can be obtained with the cryptand structure. It was shown that the significant improvement in complexation was the result of the combination of the preorganization of the cryptand hosts and the introduction of additional and optimized binding sites. Furthermore, it was demonstrated that improved complexation of bis(secondary ammonium) and bisparaquat salts could also be achieved by the formation of the pseudocryptand structure. We also prepared two dimers of inclusion cryptand/paraquat complexes driven by dipole-dipole and face-to-face p-stacking interactions. An interesting complex based on dibenzo-24-crown-10 and diquat was prepared. In its crystal structure the diquat guest lies in the concave cavity provided by two dibenzo-24-crown-8 hosts. Monopyridinium-based [2]- and [3]-pseudorotaxanes were prepared based on the newly discovered bis(m-phenylene)-32-crown-10/monopyridinium salt and cryptand/monopyridinium salt recognition motifs. Inspired by the formation of solid-state taco complexes between bis(m-phenylene)-32-crown-10 and paraquat derivatives, we designed and synthesized the first cylindrical bis(crown ether) host for paraquat derivatives and studied its complexation with paraquat. We prepared three slow-exchange C3-symmetric inclusion complexes based on a newly discovered cryptand/trispyridinium recognition motif, in which 1,3,5-trispyridiniumbenzene salts act as guests. Finally the application of several new and known recognition motifs in the preparation of a supramolecular poly[3]pseudrotaxane, and the first pseudorotaxane-type supramolecular star-shaped polymer, and the first supramolecular hyperbranched polymer was discussed.
- Pseudorotaxanes and Supramolecular Polypseudorotaxanes Based on the Dibenzo-24-Crown-8/Paraquat Recognition MotifHuang, Feihe (Virginia Tech, 2003-08-28)The research presented in this thesis focused on pseudorotaxanes and supramolecular polymers based on a new recognition motif, the dibenzo-24-crown-8/paraquat recognition motif. Main kinds of pseudorotaxanes and rotaxanes and various protocols used for the study of them were discussed first. By preparation and characterization of a series of pesudorotaxanes based on DB24C8 and paraquat derivatives, it was found that these complexes were stabilized by N+...O interactions, C-H...O hydrogen bonding, and face-to-face p-stacking interactions. Because methyl protons of paraquat are involved in hydrogen bonding to the host, the substitution of any methyl hydrogen on paraquat causes apparent association constant of the pseudorotaxane to decrease. The concentration dependence of apparent association constants, Ka,exp, of fast exchange host-guest systems was studied for the first time by using complexes based on viologens and crown ethers as examples. While the bis(hexafluorophosphate) salts of paraquat derivatives are predominantly ion paired in acetone (and other low dielectric constant solvents presumably) the complex based on dibenzo-24-crown-8 and paraquat is not ion paired in solution, resulting in concentration dependence of Ka,exp. However, four complexes of two different bis(m-phenylene)-32-crown-10 (BMP32C10) derivatives and bis(p-phenylene)-34-crown-10 (BPP3C10) with viologens are ion paired in solution, as shown by the fact that Ka,exp is not concentration dependent for these systems involving hosts with freer access to bound guests. X-ray crystal structures support these soluton-based assessments in that there is clearly ion pairing of the cationic guest and its PF6- counterions in the solid states of the latter four examples, but not in the former. The complexes based on the new dibenzo-24-crown-8/paraquat recognition motif are thus different from the complexes based on two old recognition motifs: the BPP34C10/BMP32C10-paraquat and DB24C8-ammonium motives. In order to compare these recognition motives further, the selectivity between two hosts, DB24C8 and BPP34C10, and two guests, dimethyl paraquat and dibenzyl ammnonium salt, was discussed. By individual and competitive complexation studies, it was demonstrated that DB24C8 is a better host than BPP34C10 for paraquat, and that paraquat is a better guest than dibenzyl ammonium salt for DB24C8. Finally the DB24C8-paraquat recognition motif was successfully applied in the preparation the first star-shaped supramolecular polymer based on a tetraparaquat guest and a DB24C8 functionalized polystyrene oligomer. A model system based on this guest and DB24C8 was also studied for comparison. It was found that the complexation in these two systems is cooperative, as are most biological complexations of multitopic species. Due to the ready availability of DB24C8 and paraquat derivatives, the new recognition motif should prove to be very valuable for self-assembly of other more sophisticated supramolecular systems.