Title: Design and Application of Triplet-Triplet Annihilation Upconversion Materials
Description: Triplet-triplet annihilation upconversion (TTA-UC) is a process which converts two low energy photons into one higher-energy excited state. TTA-UC has recently received attention for its potential application to many light driven processes, such as improving efficiency in photovoltaic devices and allowing use of low-energy light sources for in vivo applications, including bioimaging, optogenetics, and photochemotherapy. Each of these applications has a different set of energetic requirements, which has created a need for a diverse library of upconverting materials. Additionally, these applications benefit from improved upconversion efficiency in solid-state, a task that has proven challenging for the traditionally solution-phase process. Macromolecular scaffolds are a promising avenue to tune the electronic communication between chromophores and control intermolecular packing in solid-state. Herein, we report the investigation of dendrimers with annihilator-functionalized termini and linear annihilator polymers as frameworks to control local annihilator concentration and communication.

We find that multi-annihilator dendrimers exhibit higher upconversion yields at low concentrations compared to similar concentrations of monomer; however, higher generation dendrimers allow strong interchromophore coupling, which promotes parasitic excimer formation, decreasing relative upconversion yields. Linear annihilator copolymers with alternating anthracene and phenyl or naphthyl bridges had ground state optical properties predictive of interchromophore communication based on bridge connectivity, interchromophore length, and polymer planarity. Non-conjugated, naphthyl polymers were observed to be the most efficient at intramolecular TTA-UC in dilute solutions. In this dissertation, we will discuss current efforts in the field towards control and analysis of intramolecular TTA-UC through design of multi-annihilator macromolecules and novel annihilator scaffolds targeting underutilized regions of the electromagnetic spectrum. In Chapter 1, we list important factors to consider about improving TTA-UC and follow with discussion of reported macromolecular systems and their efforts towards intramolecular TTA-UC.

Chapter 2 introduces a series of non-conjugated dendrimers functionalized with anthracene annihilators on the periphery and analyzes their upconversion capabilities as a set of macromolecules with controlled molecular structure. In Chapter 3, we investigate the effect of connectivity between annihilators in alternating co-polymer systems, discussing the impact on ground state photophysical properties and upconversion efficiency. Finally in Chapter 4, we introduce an approach for using computational analysis as a high-throughput tool for identifying potential novel annihilator molecules.