Date of Award

Spring 1-1-2015

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry & Biochemistry

First Advisor

Niels H. Damrauer

Second Advisor

Tarek Sammakia

Third Advisor

Robert Parson

Fourth Advisor

Veronica Bierbaum

Fifth Advisor

Charles Musgrave

Abstract

One process that has the potential of efficiently harvesting solar energy is singlet fission (SF), a process by which one photon of light can produce two excited states. Investigations of three different series of bistetracene (BT) were used to explore the effect of symmetry on the rate and driving force of SF, as well as the electronic coupling. A dimer and the corresponding monomer were used to build a synthetic infrastructure and explore preliminary photophysics. All of the dimers were connected by one to three norbornyl bridges and exhibit various amounts of electronic coupling.

The first section of this dissertation will discuss a series of cofacial BT dimers with C2v symmetry that have one (BT1) to three (BT3) norbornyl bridges linking the two tetracene chromophores. Density functional theory calculations of BT1-BT3 were used to explore the SF driving force and the change in through-space versus through-bond contributions to the electronic coupling. The C2v symmetry was found to be unprofitable to SF, but vibrations accessible to the ground state would break the C2v symmetry. The thorough synthetic investigation of the monomeric tetracene-norbornyl bridge was developed to build a synthetic library that aided the synthesis of BT1, the first rigid SF dimer. Preliminary photophysics of BT1 and its monomer will also be described.

In the second portion of this work, the SF driving force, electronic coupling will be calculated for the second and third series of BT dimers, which are symmetry adaptations of BT1-BT3. In the second series, the orbital overlap of the norbornyl bridge and tetracene arms will be exploited by changing how the bridge and arms are connected to make dimers of C2 and Cs symmetry. In the final series, a heteroatom substitution of BT1 creates a series of C2 and Cs dimers that can be built using the synthetic infrastructure developed above. Both symmetry adapted series of BT dimers were found to lead to an increase in electronic coupling, which is expected to be productive for SF.

Share

COinS