Molecular Structure Engineering of Semiconducting Perylene Monoanhydride Diesters
Item
-
Title
-
Molecular Structure Engineering of Semiconducting Perylene Monoanhydride Diesters
-
Identifier
-
d_2009_2013:d08edb1953fa:11951
-
identifier
-
12602
-
Creator
-
Zhang, Hao,
-
Contributor
-
Shi Jin
-
Date
-
2013
-
Language
-
English
-
Publisher
-
City University of New York.
-
Subject
-
Polymer chemistry | Organic chemistry | bundled stack discotic columnar liquid crystalline | conducting polymer | perylene monoanhydride diester | structure tuning
-
Abstract
-
The last decade has witnessed a significant progress in the field of organic electronic materials and devices. Inspired by organic electronics' promising potential and wide applications, intensive research effort has been made to discover and design organic molecules which can give good performance in organic electronic devices. In this thesis, my research effort focused on two important fields of organic electronics: polyethylene oxide (PEO)-based conducting polymers and perylene monoanhydride diester (PEA)-based discotic columnar liquid crystalline (DCLC) materials. In Chapter 1, general background of PEO-based polymer electrolytes is introduced in part I. Different strategies to improve the polymer's conductivity, including block copolymers, graft copolymers and cross-linked polymers, are summarized. In part II of Chapter 1, it is the general background of DCLC materials. Representative DCLC materials based on a broad class of pi-conjugated materials such as hexabenzocoronenes (HBCs), porphyrins and perylene diimides (PDIs) are briefly reviewed. In Chapter 2, a new, efficient chemical modification method of poly (epichlorohydrin- co-ethylene oxide) (PECH-PEO) was proposed and executed. The PECH-PEO copolymer was successfully modified by oligo ethylene glycol (OEG) side chains via click chemistry. The high degree of modification and minimum chain degradation were achieved. The resulted PEO-based polymer demonstrated high room temperature (RT) ionic conductivity upon forming a lithium complex, which makes it useful as a solid electrolyte in lithium batteries. In Chapter 3, a mild, one-pot synthesis strategy to prepare PEAs containing labile functional groups is presented. Currently this is the only approach towards PEAs containing labile functional groups. Furthermore, using an asymmetrically substituted PEA as the intermediate, a tetraphilic perylene monoimide diester (PEI) that contains acid-labile functionalities was synthesized in good yield for the first time. And the fluorine-containing PEI showed highly interesting structure properties. In Chapter 4, a tert-butyl-based PEA was designed as the intermediate towards unsymmetric perylene derivatives. Unlike previous reported PEA intermediate, the tert-butyl-based PEA can be easily cyclized in an appreciably milder condition. This unique property makes it an ideal candidate for the synthesis of PEIs with acid-labile functional groups. In Chapter 5, a series of PEAs with bundled-stack discotic columnar liquid crystalline (BSDCLC) phase were synthesized and characterized. Compared to conventional DCLC materials, BSDCLC materials are structurally more robust to the occurrence of defects and therefore are expected to exhibit enhanced charge carrier characteristics. More importantly, perylene-based BSDCLC phase with single stacking mode is realized for the first time. Furthermore, our experimental data show that the self-assembly of a PEA can be effectively tuned not only by changing the branching unit, but also by changing the nature of flexible chains. Compared to alkyl chains, OEG chains can induce the BSDCLC phase of PEAs with much higher atom efficiency.;Apart from synthesis and molecular design, characterization is critical to my dissertation research. A full scope of instrumentation techniques including Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), polarized light microscopy (PLM), gel permeation chromatography (GPC), small-angle and wide-angle X-ray diffraction (XRD) have been employed. Additionally, molecular simulation has also been applied to predict and obtain details in molecular packing.;To sum up, the achievements in this research contribute an advance in the field of developing perylene-based BSDCLC materials which can be potentially used for organic electronics; and PECH-PEO based polymer electrolytes have reasonable good dimensional stability and conductivity, which are important properties for the application in lithium battery industry.
-
Type
-
dissertation
-
Source
-
2009_2013.csv
-
degree
-
Ph.D.
-
Program
-
Chemistry
