Document Type


Date of Degree

Spring 2017

Degree Name

PhD (Doctor of Philosophy)

Degree In


First Advisor

Tori Z. Forbes


Metal-organic nanotubular (MON) materials have garnered significant attention in the recent years not only due to the aesthetic architecture but also due to the interesting chemical and physical properties that have been reported for these compounds. The number of MONs reported in the literature are limited compared to metal organic frameworks due to synthetic challenges and difficulties in crystal engineering. These types of materials are of interest given their one-dimensional channels that lead to their potential application in advanced membrane technologies.

In Forbes group, a uranium-based metal-organic nanotube (UMON) was synthesized using zwitterionic like iminodiacetic acid (IDA) as the ligand. IDA ligand chelates to the U(VI) metal center in a tridentate fashion and doubly protonated IDA linker connects the neighboring uranyl moieties until it forms hexameric macrocycles. These macrocycles stack into a nanotubular array due to supramolecular interactions. Single crystal X-ray diffraction studies displayed there are two crystallographically unique water molecules that can be removed reversibly at 37 °C. UMON indicated selectivity to water, the selectivity of this material was analyzed using solvents with different polarities, sizes, and shapes. In the current body of work, dehydrated UMON crystallites were exposed to these solvents (in liquid and vapor phase) and studied using TGA coupled FTIR set up, confirming the highly selective nature of UMON. Kinetic studies were also conducted using an in-house built vapor adsorption setup confirmed the water uptake rate of the nanotube depends on the humidity of the environment. Uptake rates were estimated using a simple kinetic model and indicated enhanced hydration compared to other porous materials. One of the hypotheses regarding the interesting properties of UMON is that the uranium metal center might play a central role in the selectivity of this material. To test this hypothesis, a similar uranium based metal-organic nanotube containing 2,6-pyridine dicarboxylic acid (UPDC) as the ligand was synthesized and its properties were compared to that of the UMON material. UPDC did display some selectivity based upon size exclusion but did not exhibit the same selectivity to water that is observed for UMON. Different transition metals were also incorporated into the nanotubular structures to determine the influence of dopants on the observable properties. Only small amounts of transition metal dopants were incorporated into the structure, but it increased the stability under high humid environment. Attempts to incorporate transition metal dopants in the UPDC led to the formation of novel chain structures.


Doping, Metal-organic, Nanotubes, Rates, Uranium, Water


xxii, 166 pages


Includes bibliographical references (pages 156-166).


Copyright © 2017 Ashini Shamindra Jayasinghe

Included in

Chemistry Commons