Symmetric and non-symmetric stimuli-responsive flexible Lewis pair systems
department or school: Science, Faculty of
department or school: Chemistry, Department of
data provider: DSpace
degree campus: UBCV
creator: Arsenault, Nicole Evelyn
issued: 2022-01-31T08:00:00Z
issued: 2020
related degree: Doctor of Philosophy - PhD
degree grantor: University of British Columbia
description: Herein an investigation of the photophysical properties of stimuli-responsive molecules incorporating a triarylborane Lewis acid and phosphine oxide Lewis base pair on a bithiophene backbone, called flexible Lewis pairs (FlexLPs), is presented. The FlexLPs change conformation between the Lewis acid-base bound adduct form and unbound open form with surrounding solvent, where strongly hydrogen bond donating solvent stabilizes the open form through formation of a hydrogen bond with the Lewis base. The ability to synthesize diverse stimuli-responsive molecular motifs incorporating FlexLPs is achieved by installing a reactive terminal alkyne functional group on a FlexLP molecule. The application of this FlexLP molecule as a versatile stimuli-responsive ligand that can be incorporated into more complex molecular architectures, such as dimers, transition-metal complexes, and functionalized nanoparticle materials, is thus demonstrated by utilizing different alkyne coupling chemistry. Synthesis of a dimeric molecule with two FlexLP pairs connected through a conjugated bithiophene-alkyne-alkyne-bithiophene backbone is described and compared to a monomeric FlexLP molecule. The monomer and dimer FlexLP demonstrate changing emission colours and lifetimes with varying solvent, proposed to be from a change in FlexLP conformation. In the closed form a π–π* energy transition occurs resulting in blue-green emission colour, while in the unbound form a charge transfer event occurs resulting in yellow-orange emission colour. Monometallic and bimetallic Pt(terpyridine)-containing complexes functionalized with the FlexLP ligand are explored as solvent-responsive optical switches. A low energy CT band between the acid-base pair ligand and terpyridine ligand appears for both complexes, Absorption spectroscopy reveals this CT band is solvent- and temperature-responsive, and is dependent on the FlexLP ligand conformation. Investigation of the photophysical properties of two emissive Pt-functi…
aggregated CHO: https://circle.library.ubc.ca/rest/handle/2429/75192
note: SYMMETRIC AND NON-SYMMETRIC STIMULI-RESPONSIVE FLEXIBLE LEWIS PAIR SYSTEMS by Nicole Evelyn Arsenault B.Sc., University of Prince Edward Island, 2015 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in THE FACULTY OF GRADUATE AND POSTDOCTORAL STUDIES (Chemistry) THE UNIVERSITY OF BRITISH COLUMBIA (Vancouver) July 2020 © Nicole Evelyn Arsenault, 2020 ii The following individuals certify that they have read, and recommend to the Faculty of Graduate and Postdoctoral Studies for acceptance, the dissertation entitled: Symmetric and Non-Symmetric Stimuli-Responsive Flexible Lewis Pair Systems submitted by Nicole Evelyn Arsenault in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry Examining Committee: Michael Wolf, Chemistry Supervisor Zachary Hudson, Chemistry Supervisory Committee Member W. Russell Algar, Chemistry University Examiner Derek Gates, Chemistry University Examiner Additional Supervisory Committee Members: Chris Orvig, Chemistry Supervisory Committee Member Martin Tanner, Chemistry Supervisory Committee Member iii Abstract Herein an investigation of the photophysical properties of stimuli-responsive molecules incorporating a triarylborane Lewis acid and phosphine oxide Lewis base pair on a bithiophene backbone, called flexible Lewis pairs (FlexLPs), is presented. The FlexLPs change conformation between the Lewis acid-base bound adduct form and unbound open form with surrounding solvent, where strongly hydrogen bond donating solvent stabilizes the open form through formation of a hydrogen bond with the Lewis base. The ability to synthesize diverse stimuli-responsive molecular motifs incorporating FlexLPs is achieved by installing a reactive terminal alkyne functional group on a FlexLP molecule. The application of this FlexLP molecule as a versatile stimuli-responsive ligand that can be incorporated into more complex molecular architectures, such as dimers, transition…
has type: Thesis/Dissertation
date issued: 2020-11
is shown at: 10.14288/1.0392422
language: eng
degree discipline: Chemistry
provider: Vancouver : University of British Columbia Library
publisher: University of British Columbia
rights: Attribution-NonCommercial-NoDerivatives 4.0 International
rights URI: http://creativecommons.org/licenses/by-nc-nd/4.0/
scholar level: Graduate
type: Text
identifier URI: http://hdl.handle.net/2429/75192