University of Illinois Urbana-Champaign

Photophysics Of A Rigid Macrocycle Fe Complex With A Nanosecond Lifetime Mlct Excited State

Malme, Justin Thomas

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WC08_1.pptx
6479.pdf

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https://hdl.handle.net/2142/116906

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Title
Photophysics Of A Rigid Macrocycle Fe Complex With A Nanosecond Lifetime Mlct Excited State
Author(s)
Malme, Justin Thomas
Contributor(s)
  • Ren, Tong
  • Vura-Weis, Josh
  • Clendening, Reese
  • Ash, Ryan T.
Issue Date
2022-06-22
Keyword(s)
Electronic structure, potential energy surfaces
Abstract
Replication of the long lifetimes of 4d transition metal complexes in their 3d counterparts is desirable for both cost reduction and environmental concerns. Fe\textsuperscript{II}(rac-HMTI)(CN)$_{2}$ is an Fe\textsuperscript{II} complex with a remarkable nanosecond lifetime metal-to-ligand charge transfer (MLCT) state in low polarity solvents. Architecturally, the Fe\textsuperscript{II} center is ligated to axially-oriented strong field cyano ligands, and equatorially to a rigid [14]-tetracene-N4 macrocycle. This rigidity enforces poor vibrational overlap of excited states, significantly raising the barrier of vibrational relaxation and extending their lifetimes. Fe(HMTI)(CN)$_{2}$ is studied by optical transient absorption, and spectroelectrochemical studies reproduce the features of the OTA at potentials consistent with metal oxidation and ligand reduction, confirming the attribution of MLCT character to the transition. DFT, TDDFT and CASSCF computational methods are also used to create a theoretical potential energy manifold, to better describe the deactivation mechanism of the excited state. Further understanding of this molecule's photophysics will allow for more targeted development of longer-lived Fe\textsuperscript{II} complexes.
Publisher
International Symposium on Molecular Spectroscopy
Type of Resource
text
Genre of Resource
Conference Paper / Presentation
Language
eng
Handle URL
https://hdl.handle.net/2142/116906
DOI
https://doi.org/10.15278/isms.2022.WC08
Copyright and License Information
Copyright 2022 held by the authors

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Abstracts & Presentations - 2022 International Symposium on Molecular Spectroscopy PRIMARY