Alexandria Digital Research Library

Efficient methods for the synthesis of functional organic materials

Author:
Robb, Maxwell James
Degree Grantor:
University of California, Santa Barbara. Chemistry
Degree Supervisor:
Craig J. Hawker
Place of Publication:
[Santa Barbara, Calif.]
Publisher:
University of California, Santa Barbara
Creation Date:
2014
Issued Date:
2014
Topics:
Chemistry, Organic
Genres:
Online resources and Dissertations, Academic
Dissertation:
Ph.D.--University of California, Santa Barbara, 2014
Description:

The development of efficient methods for preparing well-defined, functional materials has broad-reaching implications across a number of scientific disciplines and is a critical step toward enabling technological innovation. A variety of useful strategies have been established that facilitate access to a diverse range of polymers and small molecules. These synthetic contributions as well as the properties and applications of the materials are presented.

So called 'click' chemistries including the quintessential copper-catalyzed cycloaddition between azides and alkynes (CuAAC) and coupling between thiol and alkene partners (thiol-ene) represent two of the most successful chemical transformations in modern polymer chemistry. New methods that take advantage of these tools have been developed that provide efficient routes to remarkably diverse materials including dendrimers and functional polymer nanoparticles. Specifically, high molecular weight dendrimers up to the sixth generation were prepared using an orthogonal strategy that combines both CuAAC and thiol--ene chemistry and permits complete growth and purification of each generation in rapid succession. Similarly, well-defined block copolymers containing an alkyne-functional, biodegradable block were synthesized and conjugated with various azide-containing molecules. From these multifunctional block copolymers, a new class of delivery vehicles based on self-assembled polymer nanoparticles could be accessed with release of the covalently attached payload being triggered by degradation of the polymer scaffold.

Conjugated polymers and small molecules represent another class of important materials with myriad applications that range from organic electronics (OPVs, OLEDs, etc.) to biosensors. Advancements in molecular building blocks and innovative design strategies for preparing functional materials like conjugated block copolymers are described. The preparation of end-functional donor-acceptor conjugated polymers is also demonstrated, exemplified using unsymmetrical perylene diimide derivatives for which an efficient synthetic methodology was concurrently developed. In addition, two libraries of stimuli-responsive conjugated polymers based on azulene were investigated and illustrate a new design principle in which optoelectronic properties can be systematically modulated simply by controlling the regiochemistry of the constituent building blocks.

Physical Description:
1 online resource (371 pages)
Format:
Text
Collection(s):
UCSB electronic theses and dissertations
ARK:
ark:/48907/f3s75dgg
ISBN:
9781321349979
Catalog System Number:
990045117480203776
Rights:
Inc.icon only.dark In Copyright
Copyright Holder:
Maxwell Robb
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