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Theses Doctoral

Molecular Syntheses of Extended Materials

Paley, Daniel W.

Bottom-up molecular synthesis is a route to chemically and crystallographically uniform polymers and solid-state materials. Through the use of molecular precursors, we gain atomic-level control of functionality and fine-tuning of the collective properties of materials. This dissertation presents two studies that demonstrate this approach.
Ring-opening alkyne metathesis polymerization is a possible approach to monodisperse conjugated polymers, but its applications have been limited by difficult syntheses and high air sensitivity of known organometallic ROAMP initiators. We designed a dimeric, air-stable molybdenum alkylidyne with a tris(phenolate) supporting ligand. The precatalyst is activated by addition of methanol and polymerizes cyclooctynes with excellent chemical selectivity and functional group tolerance.
The Nuckolls and Roy groups have introduced a new family of solid-state compounds synthesized from cobalt chalcogenide clusters Co6Q8(PR3)6 and fullerenes. The first examples of these materials crystallized in superatom lattices with the symmetry of simple inorganic solids CdI2 (P-3m1) and NaCl (Fm-3m). This dissertation reveals that further members of the family feature extraordinary diversity of structure, including a pseudo-trigonal array of fulleride dimers in [Co6Te8(PEt3)6]2[C140][C70]2 and a heterolayered van der Waals cocrystal [Co6Se8(PEt2phen)6][C60]5. In addition to these unusual crystal structures, this dissertation presents a method for assigning redox states from crystallographic data in Co6Q8 clusters.
Finally, a detailed guide to the collection and solution of single-crystal X-ray data is presented. The guide is intended for independent study by new crystallographers.

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More About This Work

Academic Units
Chemistry
Thesis Advisors
Nuckolls, Colin P.
Degree
Ph.D., Columbia University
Published Here
July 21, 2015