Carbon-carbon bond formation methods for the preparation of shape-persistent architectures

Finke, Aaron D.

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https://hdl.handle.net/2142/24225 Copy

Description

Title

Carbon-carbon bond formation methods for the preparation of shape-persistent architectures

Author(s)

Finke, Aaron D.

Issue Date

2011-05-25T15:02:41Z

Director of Research (if dissertation) or Advisor (if thesis)

Moore, Jeffrey S.

Doctoral Committee Chair(s)

Moore, Jeffrey S.

Committee Member(s)

• White, Maria C.
• Zimmerman, Steven C.
• Gruebele, Martin

Department of Study

Chemistry

Discipline

Chemistry

Degree Granting Institution

University of Illinois at Urbana-Champaign

Degree Name

Ph.D.

Degree Level

Dissertation

Keyword(s)

• Shape-persistent
• Macrocycles
• Carbon-carbon bond formation
• C-H activation
• Palladium
• Supramolecular
• Crystallography

Abstract

Carbon-rich, conjugated organic scaffolding is a popular basis for functional materials, especially for electronic and photonic applications. However, synthetic methods for generating these types of materials lack diversity and, in many cases, efficiency; the insistence of investigators focusing on the properties of the end product, rather than the process in which it was created, has led to the current state of the relatively homogeneous synthetic chemistry of functional organic materials. Because of this, there is plenty of room for improvement at the most basic level. Problems endemic to the preparation of carbon-rich scaffolding can, in many cases, be solved with modern advances in synthetic methodology. We seek to apply this synthesis-focused paradigm to solve problems in the preparation of carbon-rich scaffolds. Herein, the development and utilization of three methodologies: iridium-catalyzed arene C-H borylation; zinc- mediated alkynylations; and Lewis acid promoted Mo nitride-alkyne metathesis, are presented as improvements for the preparation of carbon-rich architectures. In addition, X-ray crystallographic analysis of two classes of compounds are presented. First, an analysis of carbazole-containing arylene ethynylene macrocycles showcases the significance of alkyl chain identity on solid-state morphology. Second, a class of rigid zwitterionic metal-organic compounds display an unusual propensity to crystallize in the absence of inversion symmetry. Hirshfeld surface analysis of these crystalline materials demonstrates that subtle intermolecular interactions are responsible for the overall packing motifs in this class of compounds.

Graduation Semester

2011-05

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http://hdl.handle.net/2142/24225

Copyright and License Information

Copyright 2011 Aaron D. Finke

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