Doctoral Dissertations

Abstract

Highly dipole-parallel aligned donor-acceptor substituted organic molecules are attractive for a wide array of applications, including nonlinear optics. However, only a limited number of crystals are known to adopt polar non-centrosymmetric space groups. The concepts guiding the fabrication of these polar materials have been described. The study focused on unsymmetrical donor-acceptor substituted azines and butadiene's. An improved design over (MeO, Y)-azines led to the realization of three crystals perfectly aligned in dipole parallel orientation for (PhO, Y)-azines with Y = Cl, Br, I, and one nearly perfectly aligned crystal for Y = F (Paper I). The unique bonding properties associated with fluorine enabled the realization of both polar and non-polar PBAM stacking in (PhO, F)-azine (Paper II). The symmetrical azines were also studied extensively to understand the intermolecular interactions in azine crystals. Symmetry reduction of symmetrical (X, X)-azine molecules in idioteloamphiphile monolayers (IAMs) was observed, and an explanation based on interaction inventory analyses is discussed (Paper III). Additionally, the synthesis of four representatives of the new "methoxyphenyl series" of acetophenone azines, (MeO-Ph, Y)-azines is successfully described. The methoxyphenyl chromophore offers significantly improved nonlinear optical (NLO) performance compared to the methoxy and phenoxy series (Paper IV). Furthermore, a series of 1-(4’-halophenyl)-4-(4”-methoxyphenyl) but a-1,3-dienes with halogens was synthesized. (MeO, Y)-butadiene's exhibit much higher first-order molecular hyperpolarizabilities than their analogous (MeO, Y)-azines due to their higher dipole moments and larger conjugation lengths (Paper V).

Advisor(s)

Glaser, Rainer, 1957-

Committee Member(s)

Winiarz, Jeffrey G.
Stavropoulos, Pericles
Grubbs, Garry S.
Yamilov, Alexey

Department(s)

Chemistry

Degree Name

Ph. D. in Chemistry

Publisher

Missouri University of Science and Technology

Publication Date

Summer 2024

Pagination

xxiii, 299 pages

Note about bibliography

Includes_bibliographical_references_(pages 18, 37, 80, 109, 156 and 302)

Rights

©2024 Harmeet Singh Bhoday , All Rights Reserved

Document Type

Dissertation - Open Access

File Type

text

Language

English

Thesis Number

T 12439

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Included in

Chemistry Commons

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