Biomedical subjects
Publications and source records attributed to James A Wisner.
In an effort to expand the application of a new template from interpenetrated to interlocked molecular species, we report the synthesis of a new [2]rotaxane by means of both first- and second-sphere coordination of a palladium(II) dichloride subunit.
Anion templation is used to develop a general method for rotaxane synthesis. The anion-templated synthesis of three new [2]rotaxanes containing positively charged pyridinium axles and neutral isophthalamide macrocyclic components is described. The incorporation of electron withdrawing substituents, such as the nitro group, into the 5-position of an isophthalamide bis-vinyl acyclic precursor results in a significant improvement in [2]rotaxane assembly yields. Rotaxane anion binding strengths are also enhanced whilst the rotaxane's unique interlocked binding domain ensures selectivity for chloride--the templating anion--is maintained.
Linear 1,2-bis(pyridinium)ethane 'axles' and macrocyclic 24-membered crown ether 'wheels' (, and ) combine to form [2]pseudorotaxanes. These interpenetrated adducts are held together by N+...O ion-dipole interactions, a series of C-H...O hydrogen bonds and pi-stacking between electron-poor pyridinium rings of the axle and electron-rich catechol rings of the wheel. 1H NMR spectroscopy was used to identify the structural details of the interaction and to determine the thermodynamics of the binding process in solution. Analysis of nine of these adducts by single crystal X-ray crystallography allowed a detailed study of the non-covalent interactions in the solid state. A wide variety of structural changes could be made to the system. The versatility and potential of the template for the construction of permanently interlocked structures such as rotaxanes and catenanes is discussed.
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A wide range of pseudorotaxane assemblies containing positively charged pyridinium, pyridinium nicotinamide, imidazolium, benzimidazolium and guanidinium threading components, and macrocyclic isophthalamide polyether ligands have been prepared using a general anion templation procedure. In noncompetitive solvent media, coupling halide anion recognition by a macrocyclic ligand with ion-pairing between the halide anion and a strongly associated cation provides the driving force for interpenetration. Extensive solution 1H NMR binding studies, thermodynamic investigations, and single-crystal X-ray structure determinations reveal that the nature of the halide anion template, strength of the ion-pairing between the anion template and the cationic threading component, and to a lesser extent favorable second sphere pi-pi aromatic stacking interactions between the positively charged threading component and macrocyclic ligand, together with macrocyclic ring size, affect the efficacy of pseudorotaxane formation.
The first example of a [2]catenane structure to be synthesized using anion templation is described. The nature of the anion template is demonstrated to be crucial to the assembly process, with only chloride anion producing the [2]catenane in acceptable yield. Anion binding studies reveal a dramatic catenation effect on anion selectivity properties as compared to a noncatenated acyclic receptor.
A triethylphosphonium group attached to a pyridinium ethane moiety can be used as an axle for the self-assembly of [2]pseudorotaxanes and [2]rotaxanes. Although [2]pseudorotaxane formation is limited due to the bulk of the PR4+ group, [2]rotaxanes can be formed utilising 24-crown-8 ether, benzo-24-crown-8 ether and naphtho-24-crown-8 ether. The synthesis of these [2]rotaxanes and the X-ray structure of the [2]rotaxane containing a 24-crown-8 ether wheel are described. When the crown ether contains an aromatic group two possible conformational isomers exist; these are identified at low temperature by 1H and 31P NMR spectroscopy.
Formation of a [3]catenane containing dibenzo-24-crown ether wheels and a large dipyridiniumethane ring is templated by formation of a host-guest adduct between the [3]catenane and the external crown ether.
The development of an acyclic chloride anion template in which the chloride anion is coordinatively unsaturated and available for subsequent complexation to various hydrogen bond donating components is described. This template orients a neutral hydrogen bond donating ligand and a pyridinium cation orthogonally to one another. Incorporation of second-sphere interactions between the ligand and the pyridinium cation improved the efficacy of the chloride template. These results were exploited in the construction of a chloride anion-templated [2]rotaxane which, after anion template removal, was studied with regards to its anion recognition properties. Encirclement of the neutral macrocycle around the dumbbell-shaped pyridinium cation in the [2]rotaxane produced a dramatic increase in its selectivity for chloride anions as compared to the noninterlocked cation. This is interpreted as a function of the anion template used to create the [2]rotaxane superstructure.
Two thread-shaped cations, pyridinium nicotinamide and imidazolium, as their chloride and hexafluorophosphate salts, were studied with regards to complexation with hydrogen-bond-donating acyclic and macrocyclic ligands. In the latter case, the cations form pseudorotaxanes templated by the chloride anion but not hexafluorophosphate. This formation is a function of the coupling of ion-pairing between the cation and chloride anion and subsequent recognition of the anion by the macrocyclic diamide, which provides the driving force for interpenetration. We propose that this anion template principle is a general method for the construction of pseudorotaxanes and could be applied to other cationic threads, anions, and macrocyclic species.