Pi-Stack Engineering of Semiconducting Perylene Tetracarboxylic Derivatives
Item
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Title
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Pi-Stack Engineering of Semiconducting Perylene Tetracarboxylic Derivatives
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Identifier
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d_2009_2013:12aa0625830d:10953
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identifier
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11119
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Creator
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Xue, Chenming,
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Contributor
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Shi Jin
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Date
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2011
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Language
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English
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Publisher
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City University of New York.
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Subject
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Physical chemistry | Materials science | crystal engineering | organic electronics | pi-pi interaction | semiconducting
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Abstract
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In the past decades, there has been intensive research in generating novel perylene tetracarboxylic derivatives because of a vast number of applications based on their semiconducting characteristics. The properties of the new materials rely heavily on not only the single molecular structure, but also the way of molecular packing in condensed states. The formation of effective pi-stacking structures is the key issue. In this thesis, I focused in synthesizing novel perylene tetracarboxylic derivatives by attaching various substituents at the imide nitrogens. Consequently different phases appeared and exhibited different way of molecular packing. In Chapter 1, it is the general background of perylene tetracarboxylic derivatives including (a) synthesis routes, (b) optical and electronic properties, (c) the molecular packing in condensed phases or assembling in solutions; and also the introduction of condensed state phases including amorphous, crystalline and liquid crystalline (LC) phases. In Chapter 2, a series of solution processible amorphous glassy perylene tetracarboxylic diimides (PDIs) has been designed, synthesized and characterized. The pi-stacking order in the amorphous glass phase was successfully tailored by the steric means and qualitatively evaluated. In Chapter 3, the n-alkyl chain length dependence of a series of two-dimensional (2D) smectic LC PDIs has been explored. When the n-alkyl chain is no shorter than decyl group, the PDI could exhibit a novel 2D crystalline smectic LC phase. In this phase, the PDI cores microphase separate from flexible n-alkyl chains forming 2D crystalline layers. Thermoanalysis data quantitatively reveal that the n-alkyl chains in this phase have the essentially the same order as that in the isotropic liquid state. Such truly disordered n-alkyl chains effectively decouple the inter-layer molecular correlation and make the phase genuine LC. The PDI pi-stacking order in this LC phase is crystalline because it is a part of the 2D crystalline intra-layer order. Chapter 4, PDI pi-stacking order has been engineered in the crystalline phase. By introducing two structuring factors, a series of crystalline PDIs with finely tunable PDI pi-stacking order was obtained. The crystalline PDIs with exceptionally red-shifted lambda max were obtained. Several PDIs possess lambdamax values greater than any literature-reported ones. These materials can be excellent candidates in solar cell devices. In Chapter 5, new chiral main-chain PDI containing polymers were synthesized. These polymers can form intramolecular helical pi-stacks in diluted solutions. In Chapter 6, a novel synthetic route leading to unsymmetrical perylene tetracarboxylic derivatives has been developed. Based on this synthetic method, more perylene tetracarboxylic derivatives can be generated.;In my research in this thesis, not only synthesis is an important part because it provides novel materials, but the characterization is critical as well. Infrared spectroscopy, Ultra-violet, fluorescence, differential scanning calorimetry, circular dichroism, polarized light microscopy, gel permeation chromatography, X-ray diffraction including both small angle and wide angle have been used. Additionally, molecular simulation is also very useful in design and obtaining details in molecular packing.;Overall, the achievements in this research contribute a considerable advance in the field of generating semiconducting perylene tetracarboxylic derivatives which have versatile potential applications such as in solar cell devices, organic field effect transistors and light emitting diodes.
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Type
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dissertation
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Source
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2009_2013.csv
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degree
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Ph.D.
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Program
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Chemistry
