Degree Granting Department
Michael J. Zaworotko
design, metal-organic frameworks, physisorption, porous materials, topology
Metal-organic materials (MOMs) assembled from metal-based building blocks and organic linkers have attracted much interest due to their large pore dimensions and their enormous structural diversity. In comparison to their inorganic counterparts (zeolites), these crystalline materials can be easily modified to tailor pore dimensions and functionality for specifically targeted properties.
The work presented herein encompasses the development of a synthetic 2-step process for the construction of novel families of MOMs or 'platforms' and allow us exquisite design and control over the resulting network topologies. Examples of cationic mesoporous structures were initially exploited, containing carboxylate based centers connected by metal-pyridine bonds. The inherently cationic nets allowed for subsequent anion exchange which can be regarded as an elegant and easy postsynthetic modification strategy. The incorporation of different functionalities inside the channels of the networks was then demonstrated as useful in terms of carbon dioxide capture.
The scope of the 2-step process was then expanded to construction of the first trinodal MOM platform involving triangular, tetrahedral and trigonal prismatic building units: tp-PMBB-1-asc. Examples of reticular chemistry are shown which enable the formation of large and functionalized nanocages with retention of the underlying network topology. Gas adsorption studies indicate relatively high uptakes of carbon dioxide and hydrogen which, together with the use of inexpensive ligands, provide an excellent cost/performance ratio of these materials. Moreover, very high stability in organic solvents and especially in water are addressed which is a particularly challenging, but industrially relevant target in the field of Metal-Organic Materials.
The 2-step approach was also used to synthesize a new and versatile class of metal-organic materials with augmented lonsdaleite-e (lon-e-a) topology. This family of lon-e nets is built by pillaring of hexagonal 2-dimensional kagomé (kag) lattices that are in turn pillared by a trigonal prismatic Primary Molecular Building Block (tp-PMBB-1). These MOMs represent the first examples of axial-to-axial-pillared undulating kag layers and they are readily fine-tuned because the bdc2- moieties can be varied at their 5-position without changing the overall structure. This lon-e platform possesses functionalized hexagonal channels since the kag lattices are necessarily eclipsed. The effect of the substituent at the 5-positions of the bdc2- linkers upon gas adsorption, particularly the heats of adsorption of carbon dioxide and methane, were studied.
If linear dicarboxylates were instead utilized, we were able to synthesize a new and versatile class of metal-organic materials that exhibits 4,6-connected fsb topology. These networks are constructed from simple and inexpensive building units and since interpenetration is precluded, afford very high void volumes. They therefore represent ideal targets to generate a novel family of frameworks, because of the ready availability functionalized and expanded ligand derivatives. They also allow for systematic fine tuning and could ultimately provide a roadmap to ultra-high surface areas from simple building blocks.
Scholar Commons Citation
Schoedel, Alexander, "[M3(μ3-O)(O2CR)6] and Related Trigonal Prisms: Versatile Molecular Building Blocks for 2-Step Crystal Engineering of Functional Metal-Organic Materials" (2014). Graduate Theses and Dissertations.