A New Terazulenic Platform

There is a global interest in designing smaller and more efficient electronic devices, and many scientists have been pursuing the design of materials for applications in molecular electronics. One of the special interests is the design of molecular rectifiers. This thesis includes the work toward a novel rectifying molecule. A terazulenic scaffold with electron-donating and electron-withdrawing groups at odd and even positions of the azulenic constituents, respectively, is proposed. A body of theoretical, synthetic, electrochemical, and spectroscopic studies completed by the author of this thesis are discussed.Chapter I introduces the physicochemical properties of currently known mono-, linear bi-, and linear terazulenes, with special emphasis on the orbital density distributions within the highest occupied molecular orbital and the lowest unoccupied molecular orbital of azulenic compounds and on the redox profiles of azulenic derivatives in cyclic voltammetry. Chapter I also summarizes the development of molecular rectifiers and how certain molecules can exert rectification. Chapter II first introduces the new terazulenic platform proposed by the Barybin Group based on the information discussed in Chapter I, with special attention to how the distribution of azulene’s frontier molecular orbitals affect the resulting molecular orbitals of the terazulenic scaffold. Secondly, the frontier molecular orbitals of nonlinear terazulenic moieties are discussed to clarify the effects that electron withdrawing and electron donating substituents have on the highest occupied molecular orbital and lowest unoccupied molecular orbital density distribution. Thirdly, experimental data of the synthesized 1’,2-3’,2”-terazulene indicates consistency with the hypothesized properties of the terazulenic scaffold discussed in earlier sections. Lastly, synthetic progress and failures toward the target terazulenic moieties with electron donating and electron withdrawing substituents are discussed. The last chapter concludes with key points discussed in Chapter I and Chapter II while offering additional insights pertaining to future directions in the quest for accessing the new terazulenic scaffold.

Name thesis:degree_name

M.S.

Discipline thesis:degree_discipline

Chemistry

Grantor dc:publisher

University of Kansas

Year dc:date.issued

2021

Author dc:creator

• Minh, Tu Vo

Advisor dc:contributor.advisor

• Barybin, Mikhail V

• Azulene
• Molecular rectification

Language dc:language.iso

en

Dc Identifier Other

https://www.proquest.com/LegacyDocView/DISSNUM/28547632

OAI identifier oai:identifier

oai:kuscholarworks.ku.edu:1808/38252