Physical Sciences and Mathematics Commons^™

Design And Applications Of Charge-Separated Metal-Organic Frameworks, Sheela Thapa

Chemistry and Chemical Biology ETDs

Ionic tetrapodal ligands with colinear coordinating arms are very effective for designing hybrid porous materials with unusual structure and properties. The novelty of this research work lies in the utilization of a unique borate ligand that leads to charge-separated MOF structure with tailor designed properties. Borate ligands being tetrahedral afford 3D materials and the negative charge of borate anion can compensate the positive charge of metal ion in the framework. The borate ligands designed in this research consists of quaternary ammonium cation and anionic borate with four pyridine arms. These ligands upon coordination with Cu(I), Cu(II), Ag(I) and Co(II) metal …

Nontraditional Hydrogen Bonding In Asymmetric Lewis Acid Catalysis, Brandon Vernier

Electronic Theses and Dissertations

In the field of asymmetric induction, there is a shift from the synthesis of reaction

specific chiral auxiliaries towards a broader mechanistic approach. Our approach is to

develop a theory of asymmetric catalyst design from first principles. The Diels-Alder

reaction of 2-methacrolein and 1,3-cyclopentadiene in the presence of 15 mole % lmenthoxy

aluminum dichloride, reported by Koga, achieved the (S)-exo-Diels-Alder

cycloadduct with 72% ee (0% ee Endo for acrolein). The dramatic change from 72% to 0%

ee is a significant fact that has been overlooked in practical organic synthesis.

In the first phase of this work, the conformational landscape of …