In pursuit of conjugation in one-dimension: Synthetic studies of oligomeric and polymeric organic materials
Chapter 1. Ring-Opening Alkyne Metathesis Polymerization of Dibenzocyclooctynes A molybdenum(VI) propylidyne substituted with bidentate phenoxides will react with dibenzocyclooctynes in living ring-opening alkyne metathesis polymerization (ROAMP). The corresponding monodentate phenoxides do not yield well-controlled polymerizations. However, if the substrate in the ROAMP reaction is an aliphatic cyclooctyne, uncontrolled, non-living polymerizations take place in all cases. Chapter 2. Ring-Opening Alkyne Metathesis via a Tungstenatetrahedrane Intermediate A cyclopropenone-modified dibenzocyclooctyne will undergo a single ring opening alkyne metathesis reaction in the presence of Schrock's tris(tert-butoxy)tungsten(VI) neopentylidyne--a highly active alkyne metathesis catalyst. Despite the enormous amount of ring strain present in and related diphenycyclooctadiynes, these compounds do not readily undergo ring-opening alkyne metathesis polymerization (ROAMP), even with the most active alkyne metathesis catalysts available. The ring-opening of 1 proceeds via a tungstenatetrahedrane intermediate. Because of its sluggish reactivity, we were able to follow the ring-opening reaction by NMR to gain mechanistic insight into this remarkable behavior. Chapter 3. Functionaliztion of Diphenyloligoenes Bromine and carboxylic acid substituted α,ω-diphenyl-µ,ν-dicyano-oligoenes (DPDCn) were synthesized up to 9 and 7 olefin units in length, respectively. The carboxylic acid functionalized oligoenes (DPDCn-CO2H) are aligned through hydrogen bonding to DMF in the solid state. These can also be used to direct monolayer formation of Fe3O4 on single crystalline, 100 Gallium Arsenide.
Chemistry, Oligomers, Polymers, Organic compounds--Synthesis
Networked Digital Library of Theses and Dissertations