Date of Award

Spring 2011

Project Type


Program or Major

Materials Science

Degree Name

Doctor of Philosophy

First Advisor

Glen P Miller


In the present work, we studied the chemistries of acenes, cyclacenes, [60]fullerenes and CNTs. Acenes are well known organic semiconductors. Pentacene is a benchmark organic semiconductor due to low HOMO-LUMO gap and high charge carrier mobilities in its thin film. Its poor solubility and instability, however, limit its utility and overall cost effectiveness. We successfully synthesized several sulfur-functionalized acene derivatives that overcome these problems. However, we also encountered difficulties to aromatize some of these derivatives. To circumvent these problems, we studied some new synthetic routes to sulfur-functionalized anthracenes, pentacenes and nonacenes. Additionally, the electronic properties of substituted acenes were compared using high level DFT calculations. According to our unrestricted DFT calculations, significant spin characters associated with thio-substituted nonacenes are likely the reason for their instabilities and difficult syntheses. Our UV-Vis-NIR studies reveal acene characteristics in acene quinones and hydroxyacenes that are dissolved in concentrated sulfuric acid.

Cyclacenes may be useful precursors to synthesize SWNTs with uniform dimensions. We explored the supramolecular assembly of a bis[60]fullerene adduct of a 2,3,9,10-tetrasubstituted pentacene as a method to produce a [24]cyclacene framework. To that end, we synthesized the bis[60]fullerene adduct of 2,3,9,10-tetraiodomethyl-6,13-diphenylpentacene. The synthesis of a cyclacene framework via intermolecular cycloaddition of bis[60]fullerene adducts requires further study. According to our unrestricted broken symmetry calculations for different functionalized [n]cyclacenes, HOMO-LUMO gaps and spin characters are impacted by the presence and location of alkylthio and/or arylthio functional groups on the [n]cyclacene skeleton.

[60]Fullerene is known to form polysultone and chlorinated derivatives when treated with fuming sulfuric acid (FSA) and chlorosulfonic acid (CSA), respectively, at room temperature. Based on our preliminary study, we predict that MWNTs react with boiling CSA and they are unreactive toward boiling FSA. The CSA treated MWNTs showed less bundling and broken tips in their AFM and TEM images. We studied the self-assembly of carboxylated-SWNTs and polystyrene latex (PSL) particles on different substrates. We believe that carboxylated-SWNTs have stronger interactions with amino or carboxy terminated PSL than unsubstituted PSL particles. According to our SEM analysis, self-assembly of the nanocomposites is moderately substrate dependent.