Date of Award

2012

Degree Type

Dissertation

Degree Name

Ph.D.

Department

Chemistry and Biochemistry

First Advisor

Loeb, Stephen (Chemistry and Biochemistry)

Keywords

Chemistry.

Rights

CC BY-NC-ND 4.0

Abstract

The focus of this thesis is the incorporation of the 1,2-bis(pyridinium)ethane motif into new [2]rotaxane ligands for the purpose of developing new metal organic rotaxane frameworks (MORFs). Both new stoppers that can act as ligands as well as new crown ethers with appended donors were synthesized and these components combined to create new [2]rotaxane ligands and eventually new MORFs. Chapter 2, looks at the synthesis and coordination chemistry of a [2]rotaxane containing terpyridine stoppers. The [2]rotaxane was shown to form mixed ligand complexes with RuII, AgI, ZnII, and PdII. The complexes were studied in solution by NMR, and UV/vis spectroscopy and mass spectrometry and in the solid state by X-ray crystallography. Chapter 3 and 4, focuses on the synthesis of new tetrasubstituted dibenzo-24-crown-8 ethers and their inclusion into [2]pseudorotaxanes and [2]rotaxanes. The new [2]pseudorotaxanes and [2]rotaxanes were characterized in solution by NMR spectroscopy and mass spectrometry and in the solid state by X-ray crystallography. The new crown ethers were then used for the development of [2]rotaxane ligands and metal organic rotaxane frameworks. The complexes were studied in solution by NMR, and UV/vis spectroscopy and mass spectrometry and in the solid state by X-ray crystallography. Chapter 5, focuses on a new class of MORFs in which donor groups have been incorporated on to the crown ethers which allows for the [2]rotaxane ligands to link though the wheel rather than axles to propagate the coordination polymer. The highlight was formation of a coordination complex with CdII that is a 2-periodic, metal-organic rotaxane framework. The synthesis and characterization of all the species were studied by NMR spectroscopy and mass spectrometry in solution and in the solid state by X-ray crystallography. Chapter 6, looks at ways to combine chelating axles with coordinating crown ethers to form unique "combo" [2]rotaxane ligands capable of forming two independent frameworks by virtue of having coordinating groups on both components of the rotaxane. A new stopper based on a the polydentate ligand bis(2-pyridylmethyl)amine was developed for this purpose. "Combo" [2]rotaxane ligands were prepared and characterized in solution by NMR spectroscopy and mass spectrometry.

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