DOI
https://doi.org/10.25772/7VVD-2J21
Defense Date
1976
Document Type
Dissertation
Degree Name
Doctor of Philosophy
Department
Chemistry
First Advisor
Raphael M. Ottenbrite and Billy L. Stump
Abstract
Tetracyanoethylene and tetracyanoquinodimethane were reacted with various N,N-dimethyl-a, w-alkyldiamines to produce TCNE and TCNQ diamino and monoamino derivatives. NMR and ir spectra of the monoamino derivatives, 1-(N,N-dimethyl-a,w-alkyldiamino)-1,2,2-tricyanoethylenes and 7-(N,N-dimethyl-a,w-alkyldiamino)-7,8,8-tricyanoquinodimethans, indicated that these compounds exhibited strong nitrogen-hydrogen-nitrogen intramolecular hydrogen bonding. This phenomenon was corroborated by molecular weight and preliminary x-ray analyses.
The 1,1-bis(N,N-dimethyl-a,w-alkyldiamino)-2,2-dicyanoethylene and 7,7-bis(N,N-dimethyl-a,m-alkyldiamino)-8,8-dicyanoquinodimethan derivatives were polymerized with a,m-alkyldibromides containing two to six methylene groups to produce the corresponding ionene polymers. Viscosity measurements of the polymers indicated that the TCNE copolymers were generally of higher molecular weight than the corresponding TCNQ copolymers.
The two polymer series were treated with lithium tetracyanoquinodi-methanide to produce semiconducting polymers. Electrical measurements indicated that these materials had conductivities on the order of 10-7 ohm-1 cm-1. Treatment of the polymers with neutral TCNQ resulted in increased conductivities ranging from two to five orders of magnitude.
Rights
© The Author
Is Part Of
VCU University Archives
Is Part Of
VCU Theses and Dissertations
Date of Submission
4-6-2018
Comments
Scanned, with permission from the author, from the original print version, which resides in University Archives.