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Katie Campbell

Publications and source records attributed to Katie Campbell.

5 recordsLinked to original sources

Characterization of porosity in organic and metal-organic macrocycles by hyperpolarized 129Xe NMR spectroscopy.

Hyperpolarized (129)Xe NMR spectroscopy is used to establish the solid-state porosity of shape-persistent macrocycles with either an organic or metal-organic framework. These studies show that even upon removal of cocrystallized solvent molecules, the macrocycles maintain a porous or channeled structure. The technique can provide valuable information about systems for which X-ray crystallographic analysis is not feasible. [structure: see text]

Journal Article↗

Coordination-driven self-assembly: solids with bidirectional porosity.

Coordination-driven self-assembly reactions have been used in the preparation of a variety of discrete supramolecular species, some of which have shown promise as synthetic receptors. Many highly ordered coordination polymers and porous networks have been prepared in a similar fashion. While a few of these solids are capable of the uptake of small organic molecules in the resultant molecular channels, the formation of truly porous structures has frequently been thwarted by lattice interpenetration. A strategy for the formation of porous solids that may circumvent this problem is based on the covalent construction of nanoscale macrocycles which, when eclipsed in the solid state, may lead to porous, tubular assemblies. We have incorporated these concepts toward the realization of a bidirectionally porous solid. The metal-directed, self-assembly of a conjugated, macrocyclic ligand provides a discrete, supramolecular entity in solution and the solid state. X-ray crystallographic analysis establishes that this assembly packs such that bidirectional channels are realized, and the incorporation of only ClCH2CH2Cl into the crystal lattice demonstrates that these channels are potentially suitable for the selective uptake of small organic guests.

Crystallography, X-Ray↗

Functionalized macrocyclic ligands for use in supramolecular chemistry.

The synthesis of three cross-conjugated macrocycles bearing pyridine functionality is described. The ability of two of these molecules, 5a and 5c, to behave as 4,4'-bipyridine mimics in self-assembly reactions is demonstrated by axial coordination to a metalloporphyrin. The directed coordinative ability of the pyridine rings ensures predictable self-assembly into well-ordered nanoscale systems, both in solution and the solid state. 1H, 13C, and HMQC NMR spectroscopic experiments and ESI MS have been used to characterize the supramolecular complexes in solution. X-ray crystallographic analysis of solid-state assemblies 7a and 7c provides insight into the scope and flexibility of these macrocyclic ligands as supramolecular building blocks. UV-vis and fluorescence spectroscopies provide a description of their electronic characteristics.

Journal Article↗

Iterative synthesis and characterization of cross-conjugated iso-polydiacetylenes.

An iterative synthesis of cross-conjugated iso-polydiacetylenes (iso-PDAs) is reported based on three fundamental building blocks: vinyl triflates 8, 9, and 25. An efficient sequence of palladium-catalyzed cross-coupling reactions of vinyl triflates and terminal alkynes has been employed to extend the chain length of these oligomers. The longest member of the series, nonamer 19, spans 3.4 nm from Si to Si atom. The stability and solubility of the conjugated oligomers have been evaluated as a function of pendant substitution. Assessment of solid-state structural properties was achieved via X-ray crystallographic analyses of monomer 12 and trimer 14. The electronic characteristics of the monodisperse oligomers have been fully analyzed by UV-vis spectroscopy in solution and as thin films, and these studies suggest that pi-electron communication is present along the enyne framework, but quickly reaches saturation by the stage of nonamer 19.

Journal Article↗