Chemistry and Chemical Biology ETDs

Publication Date

Spring 5-12-2023

Abstract

Square-planar compounds of the (dichalcogenolene)Pt(diimine) series are possess unique photophysical properties that include long-lived excited state lifetimes, which result in their being potential candidates for numerous applications. These applications include solar energy conversion, photocatalysis, nonlinear optics, and photoluminescent probes of biological systems. The most interesting feature of the (dichalcogenolene)Pt(diimine) series of molecules is the bpydichalcogenolene ligand-to-ligand charge transfer (LL’CT) band. To better understand their photoluminescent decay mechanism, and understand their excited dark state properties, we have synthesized and characterized new compounds that include (Thp-bpy)Pt(CAT), (Thp2-bpy)Pt(CAT), (Thp-bpy)Pt(bdt), and (Thp2-bpy)Pt(bdt). Through interpretation of electronic absorption, resonance Raman, XAS, photoluminesce spectroscopy, in addition to computational results and a time dependent theory of spectroscopy analysis for these complexes, we

have added new insight into their electronic and geometric structures. This has provided a deeper understanding of the photoluminescent decay mechanism. Electron spin polarization (ESP) is an important concept in quantum information science, which can be used to overcome the small population difference between the ms states at Boltzmann equilibrium. Previous studies showed that there are several factors that could control the sign and the intensity of the ESP, such as the sign of magnetic exchange coupling, the metal ion SOC constant, and the presence of localized radical excited states. In order to better understand the mechanism for generating ESP in these complexes, we have used the MBPDZ ligand and a pendant verdazyl radical (VDZ) covalently bound to the CAT in the synthesis and characterization of (MBPDZ)Pt(CAT) , (MBPDZ)Pt(CAT-VDZ) and (MBPDZ)Pt(CAT-NN). Through interpretation of electronic absorption, EPR, and TREPR spectroscopies, in addition to computational results and a time-dependent of spectroscopy analysis for these complexes, we propose a new mechanism for the generation of the ESP in these radical elaborated molecules.

Language

English

Document Type

Dissertation

Degree Name

Chemistry

Level of Degree

Doctoral

Department Name

Department of Chemistry and Chemical Biology

First Committee Member (Chair)

Prof. Martin L. Kirk

Second Committee Member

Prof. Terefe G. Habteyes

Third Committee Member

Prof. Dongchang Chen

Fourth Committee Member

Prof. Victor M. Acosta

Download

Share

COinS