Browsing by Subject "Transient resonance Raman spectroscopy"
Now showing 1 - 1 of 1
- Results Per Page
- Sort Options
Item New aproaches to functional organic electronics : development of redox active materials for energy applications(2016-05) Mueller, Kory Michael; Humphrey, Simon M.; Rose, Michael J; Jones, Richard A; Sessler, Jonathan L; Farrell, Joshua RThe electrochemical functionalization of graphene using diaryliodonium salts was explored as a new avenue for altering the physical, chemical and electronic properties of graphene. Control of the surface density of the grafted molecules was achievable up to 2.5 x 10¹⁴ molecules∙cm⁻², and the grafting ratio of asymmetric diaryliodonium salts was shown to be unperturbed by the electronic nature of the aryl rings. Scanning Tunneling Microscopy coupled with Density Functional Theory calculations provided valuable insight into the mechanism by which the molecular grafting process is controlled. Two bisphosphine ligands were synthesized to explore their ability to support light emission in copper(I) complexes. The ligand 3,4-bis(diphenylphosphino)thiophene was shown to efficiently promote thermally activated delayed fluorescence, while (5,5'-dimethyl-[2,2'-bithiophene]-3,3'-diyl)bis(diphenylphosphane)-supported complexes were found to exhibit dual emission and luminescent thermochromism. A rare example of electronic communication between rhodium centers bridged by 9,10-diisocyanoanthracene was observed. Through the performed studies, it was shown that the electronic nature of the ligand trans- to the molecular bridge plays a critical role in facilitating communication. Switching from a neutral PNP pincer ligand to an anionic, cyclometallated PCP pincer ligand raised the energy of the lower lying occupied molecular orbitals with respect to the singly occupied molecular orbital, and inverted the energetic ordering of the rhodium-based d-orbitals to better facilitate electronic communication though the system. The triplet state in organic photovoltaic devices has become increasingly more important in improving device efficiencies. To better understand the triplet excited state in polythiophene based materials, a library of oligothiophenes has been synthesized. The photophyscial and electrochemical properties of these materials have been cataloged and studies into the structure and delocalization of the triplet exciton using transient resonance Raman spectroscopy have been performed. Finally, a novel separation system for nuclear waste remediation consisting of ionophoric ligands chemically tethered to a conducting polymer core have been synthesized. These systems were shown to reversibly coordinate Th(IV) ions from solution based on the oxidation state of the polymer core. Furthermore, these systems were shown to undergo multiple extraction cycles and exhibit selective ion extraction.