Doctoral Dissertations

Keywords and Phrases

Cucurbiturils

Abstract

"From a practical perspective, host-guest complexes are vehicles for understanding and using supramolecular interactions for purposeful function in sensors, molecular machines and switches, while from a fundamental perspective they may lead to novel supramolecular protection schemes in basic organic reactions. This dissertation examines the interactions of cucurbiturils as barrel-shaped hosts, exhibiting a hydrophobic cavity, with substituted benzoylpyrydinium, phenypyrylium, and diazaanthraquinonediium cations as guests. In water, N-methyl-4-(p-substituted benzoyl)pyridinium cations exist in equilibrium with their hydrated forms (gem-diols), whose concentrations depend on the para substituent. In the presence of cucurbit7uril (CB[7]), the benzoyl group shows a preference for the CB[7] cavity, and the ketone to gem-diol equilibrium is shifted toward the keto form, meaning that the stabilization through hydrophobic interactions of the benzoyl group in the CB[7] cavity exceeds the hydrogen bonding stabilization of the gem-diols in the aqueous environment. In an aprotic polar solvent such as dimethylsulfoxide, 4-benzoylpyridinium cations undergo heterogeneous electron transfer simultaneously from both their free state as well as their complexes with CB[7]. In the same line of work, N,N'-dimethyl-2,6-diaza-9,10-anthraquinonediium dication in water not only exists in equilibrium with its gem-diol but also forms aggregates which cause line-broadening in ¹H NMR. At low pH (<1), the aggregates break up and the equilibrium is shifted exclusively toward the quinone form. In the presence of CB[7], the quinone form undergoes inclusion with CB[7] by slow exchange in both water and aqueous acid. Both free and CB[7]-intercalated quinone forms are observed by ¹H NMR. To gain more insight on the intercalation of monocationic guests in the cucurbituril cavity not only as a function of their hydrophobic properties but also in terms of their shape, size and the size of the cavity, 4-phenylpyrylium cation (Pylm) was chosen as a guest and both CB[7] and CB[8] as hosts. The size and shape of the guest was modified by 2,6-substitution (Me, iPr, Ph, t-Bu). In water, 2,6-disubsituted-Pylm form dimers, but they enter as such only in CB[8]. All guests insert their 4-phenyl groups in either cavity, except (iPr-Pylm)₂@CB[8] where iPr-groups are inserted. Stereochemistry is interpreted by an interplay of size and hydrophobicity of pyrylium substituents, solvation effects, and size and flexibility of the hosts"--Abstract, page iv.

Advisor(s)

Leventis, Nicholas
Sotiriou-Leventis, Lia

Committee Member(s)

Winiarz, Jeffrey G.
Chandrashekhara, K.
Stavropoulos, Pericles

Department(s)

Chemistry

Degree Name

Ph. D. in Chemistry

Sponsor(s)

Missouri University of Science and Technology. Department of Chemistry
Missouri Research Board
National Science Foundation (U.S.)

Publisher

Missouri University of Science and Technology

Publication Date

Spring 2010

Journal article titles appearing in thesis/dissertation

  • Control of the ketone to gem-diol equilibrium by host-guest interactions
  • Simultaneous electron transfer from free and intercalated 4-benzoylpyridinium cations in cucurbit[7]uril
  • Control of quinone to gem-diol equilibrium by interactions with cucurbit[7]uril
  • Factors at play in the orientation of pyrylium guests in cucurbituril hosts

Pagination

xvii, 137 pages

Note about bibliography

Includes bibliographical references.

Rights

© 2010 Arumugam Thangavel, All rights reserved.

Document Type

Dissertation - Open Access

File Type

text

Language

English

Library of Congress Subject Headings

Charge exchange
Glycols
Pyrylium compounds

Thesis Number

T 9647

Print OCLC #

747503443

Electronic OCLC #

747504369

Included in

Chemistry Commons

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