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Clark Lecture Series, Elizabeth Young, Lehigh Univers

From Photodynamic Therapy to Controlling Excited- State Dynamics with Protons: Photophysics of  Pd(II)biladiene, Azo Dyes, and Re(I)carbonyl complexes

Host: PLU

Elizabeth R. Young, Ph.D.

Associate Professor

Department of Chemistry

Elizabeth Young

Solar light harvesting and interconversion of solar energy into either electricity or drivingforce for small molecule activation reactions are critical to the production of energy andother processes that our society requires to function. In this talk, I will discuss three projectsunited by photochemistry, each with their own application. In the first vignette, I will discussa porphyrinoid complex, called a Pd(II)biladiene, This Pd(II)biladiene moiety was designedfor use as a photosensitizer drug for photodynamic therapy. Up until this point, the excited-state dynamics of such biladiene complexes have been virtually unexplored. During our workon this moiety, we discovered that while excitation into the lowest-energy absorption featureof the Pd(II)biladiene complexes produces expected photophysics, interestingly, excitationinto higher-lying excited states resulted in an additional, unexpected lifetime. I will discussour work to propose the cause of this unexpected behavior. In the second vignette, I willdiscuss our recent work on a ubiquitous industrial dye that is a major cause of pollution indeveloping countries. Azo dyes are a class of organic molecules defined by an N=N doublebond connecting two aromatic moieties. They are the single most common dyes used inindustrial processes, found in everything from colorants and cosmetic additives to textilereagents, biologic indicators, and organic synthons. They present a significant pollutionproblem because untreated dyes released into waterways can be ingested and are toxic tohumans and animals. Our recent studies shed light on their photophysics and how we canmanipulate their photophysical evolution. In the third vignette, I will discuss a Re-carbonylcomplex that we designed for use in excited-state proton-coupled electron transfer (PCET)mechanistic investigations. PCET mechanisms can be employed to improve energetic andkinetic favorability of chemical transformations or to direct chemical reactivity, and we canseek additional energetic advantage by using solar energy to drive such coupled reactions.This Re-carbonyl complex has demonstrated an unexpected photophysical dependence onthe ligand protonation state that we rationalize using density functional theory calculations.