Title

ULTRAFAST EXCITED STATE RELAXATION DYNAMICS OF ELECTRON DEFICIENT PORPHYRINS: CONFORMATIONAL AND ELECTRONIC FACTORS

Date of Award

2005

Document Type

Dissertation

Degree Name

Doctor of Philosophy (Ph.D.)

Department

Photochemical Sciences

First Advisor

Michael Rodgers

Abstract

Metallo-tetrapyrroles (MTP) are highly stable macrocyclic ð-systems that display interesting properties that make them potential candidates for various applications. Among these applications are optoelectronics, magnetic materials, photoconductive materials, non-linear optical materials and photo tumor therapeutic drugs. These applications are generally related to their high stability and efficient light absorption ability in the visible and near-infrared region of the optical spectrum. Metallo porphyrins are well known and widely studied representatives of metallotetrapyrroles. Electron deficient substituents in the meso positions are well known to greatly influence the interaction between the metal d-orbitals and the nitrogen orbitals of the tetrapyrrole macrocycle. In this work, a series of electron deficient porphyrins has been studied to gain some knowledge about the change in the excited state dynamics with structural and electronic modifications. Among these porphyrins is nickel and iron modified species bearing perfluoro-, perprotio-, p-nitrophenyl- and perfluorophenyl- meso substituents. Ultrafast transient absorption spectrometry has been used as the main research instrument along with other spectroscopic and electrochemical methods.