Synthesis, Characterization, and Photophysical Properties of Novel Conformationally Dynamic Copper Complexes

Urbain, Lucia

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https://hdl.handle.net/2142/133272 Copy

Description

Title

Synthesis, Characterization, and Photophysical Properties of Novel Conformationally Dynamic Copper Complexes

Author(s)

Urbain, Lucia

Issue Date

2026-05-15

Director of Research (if dissertation) or Advisor (if thesis)

Olshansky, Lisa

Department of Study

Chemistry

Degree Granting Institution

University of Illinois at Urbana-Champaign

Degree Name

B.S. (bachelor's)

Degree Level

Thesis

Keyword(s)

Photoinduced Charge Transfer, Copper Photosensitizers, Charge Separated State, Conformational Dynamicity

Language

eng

Abstract

The conversion of solar energy remains one of the most important challenges in the quest to develop sustainable, renewable energy resources. Metal complex photoredox catalysis is a promising method for the conversion of solar energy into chemical energy. Ruthenium, iridium, and platinum complexes with rigid ligands have been the state-of-the-art photocatalysts for decades. However, they are expensive and potentially hazardous. Copper complexes with flexible ligands provide a favorable first row transition metal alternative because they do not exhibit fast nonradiative decay of metal-to-ligand-charge-transfer excited states from low-lying metal centered states. Dipicolylaniline ligands with a methoxy chelating group (dpaOMe), capable of stabilizing CuI and CuII, and a light harvesting fluorophore (BODIPY), have shown interesting photophysical properties. The CuI complex can undergo photoinduced electron transfer, where an electron transfers from the CuCl(dpaOMe) donating group to the BODIPY accepting group, to form a longlived charge separated state with potential photocatalytic abilities. During this process CuI oxidizes to CuII , and undergoes a Jahn-Teller distortion where the pseudo-tetrahedral geometry distorts to a square pyramidal geometry. This conformational dynamicity is inspired by the entatic state seen in blue copper proteins that perform electron transfer. Electron transfer theories suggest that increasing the distance between the electron donor and acceptor may indirectly increase the lifetime of the charge separated state. This thesis presents a new modification to the dpaOMeBODIPY ligand with the addition of a phenyl linker between the dpaOMe ligand core and the BODIPY fluorophore, which increases the donor/acceptor distance. This aims to lengthen the charge separated state lifetime and improve potential photocatalytic ability. The synthesis, characterization, and photophysical properties of dpaOMePhBODIPY, and it’s copper complexes, CuCl(dpaOMePhBODIPY) and [CuCl(dpaOMePhBODIPY)]PF6, are 3 explored in detail. Comparisons between the systems with and without the phenyl linker are also discussed.

Type of Resource

text

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