Graduation Year

2004

Document Type

Dissertation

Degree

Ph.D.

Degree Granting Department

Chemistry

Major Professor

Zaworotko, Michael J.

Keywords

Coordination polymers, Isophthalic acid, SBU, Paddlewheel, Crystal engineering

Abstract

Supramolecular synthesis has gained much attention in recent years. Such an approach to synthesis represents an attractive alternative to traditional, multi-step synthesis, especially for making complex, nanoscopic structures. Of particular interest, in the context of this work, is the use of metal-organic interactions to direct the self-assembly of nanoscopic architectures. These interactions are highly directional, relatively "strong" (compared to other supramolecular interactions) and kinetically labile, which allows for "self-correction" and in turn the production, often in high yield, of defect-free products. This also means that a number of related, yet structurally diverse products (supramolecular isomers) could be isolated.

The work presented herein demonstrates the supramolecular synthesis of related, yet structurally diverse family of metal-organic nanoscale supramolecular architectures that are based on the ubiquitous paddle-wheel dimetal tetracarboxylate secondary building unit (SBU) and angular dicarboxylate ligands. It also demonstrates that the SBU self-assembles into clusters of four (tetragonal) and three (trigonal) nanoscale secondary building units (nSBU), which further self-assemble into nanoscale structures that include discrete (0D) faceted polyhedra, tetragonal 2D sheets and another 2D sheet that conforms to the so-called Kagom lattice. In addition, the work herein demonstrates that synthesis under thermodynamic equilibrium conditions facilitates "self-correction" so that the most stable thermodynamic product is obtained. Synthesis, characterization and crystal structure analysis of these structures is presented herein.

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