Type
Text
Type
Thesis
Advisor
Lauher, Joseph | Goroff, Nancy S | Rudick, Jonathan.
Date
2013-12-01
Keywords
diiodobutadiyne, polymer, synthesis | Chemistry
Department
Department of Chemistry.
Language
en_US
Source
This work is sponsored by the Stony Brook University Graduate School in compliance with the requirements for completion of degree.
Identifier
http://hdl.handle.net/11401/77125
Publisher
The Graduate School, Stony Brook University: Stony Brook, NY.
Format
application/pdf
Abstract
Conjugated organic polymers have optical and electronic properties that make them candidates for applications in organic field effect transistors (OFETs) and light emitting materials. Polydiacetylenes (PDAs) are an important branch of conjugated polymers with alternating poly(ene-yne) structure. The all-carbon polymer without any side groups is carbyne, which has only alternating single and triple carbon-carbon bonds. Carbyne provides a good opportunity to investigate the inherent properties of conjugated polymers. Polydiiododiacetylene (PIDA), a simple PDA with only iodine atom substituents, can be successfully obtained by the topochemical polymerization of the monomer diiodobutadiyne. This polymerization is achieved through the use of bis(nitrile) or bis(pyridyl) hosts, which hold the monomer in the correct orientation for polymerization by a halogen bond between the Lewis-basic nitrogen and the Lewis-acidic iodine. With the goal of forming carbyne, PIDA has been partially dehalogenated by Lewis bases such as pyrollidine, however, inter-and intramolecular aggregation prevented full dehalogenation. In this project, an innovative macrocyclic host-guest framework was designed and evaluated for the preparation of PIDA. The macrocyclic host has the function of keeping individual PIDA strands separate and elongated so that Lewis bases can access all the iodine. The macrocyclic host should be able to self-assemble into a tubular framework with enough inner space to accommodate the monomer, diiodobutadiyne. This host should also possess a nitrogen group that can weakly interact with the monomer to hold it in place. Finally, the host should have solubility commensurate with the monomer, since co-crystallization is carried out by slow evaporation. Several possible designs were proposed and computational modeling was performed to analyze the relation between conformation and ring size, as well as whether or not there is a need for a rigidity-increasing segment and a solubility-increasing segment. Based on the evaluation, the target molecule was selected for synthesis. Several steps have been optimized in the synthesis of the macrocyclic host, including hydroxylation and PEG-tosylation of 2,6-dibromopyridine, followed by a Sonogashira coupling with an alkyne-functionalized phthalimide group. Hydrazinolysis was attempted on a model compound and the host precursor to convert the phthalimide group into the amine. Several other detour routes were considered, including Boc protection on the amine before Sonogashira coupling. | 73 pages
Recommended Citation
Liu, Xianzhi, "Macrocyclic Host-Guest Framework for Polymerization of Diiodobutadiyne" (2013). Stony Brook Theses and Dissertations Collection, 2006-2020 (closed to submissions). 2961.
https://commons.library.stonybrook.edu/stony-brook-theses-and-dissertations-collection/2961