University of Illinois Urbana-Champaign

Gas-phase infrared spectroscopy of metal-ligand redox pairs

Munshi, Musleh Uddin

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1080815.pptx
2945.pdf

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https://hdl.handle.net/2142/100708

Description

Title
Gas-phase infrared spectroscopy of metal-ligand redox pairs
Author(s)
Munshi, Musleh Uddin
Contributor(s)
  • Oomens, Jos
  • Martens, Jonathan K.
  • Berden, Giel
Issue Date
2018-06-20
Keyword(s)
Mini-symposium: Far-Infrared Spectroscopy
Date of Ingest
  • 2018-08-17T16:09:34Z
  • 2018-12-12T22:37:37Z
Abstract
Transition metal organometallic complexes are known for their catalytic activation of small molecules. For example, CO2 activation by Ni1+(cyclam) complexes has recently been reported in the gas-phasea , where the oxidation state of the metal appeared to be the key for the electrochemical reduction of CO2. In this contribution, we show that metal(II) complexes, including Ni-cyclam, generated via electrospray ionization can be charge reduced inside a quadrupole ion trap mass spectrometerb (QIT MS) via an electron transfer reduction (ETR) reaction using fluoranthene radical anions as reagentsc . Moreover, their IR spectra can be recorded by action spectroscopy using the FELIX free electron laser, which enables their structural characterization. The complex in either of two charge states is isolated by its m/z, stored and irradiated with tunable IR light in the range of 500-1800 cm−1 . IR induced dissociation occurs upon resonant vibrational excitation of the trapped ions, so that an IR spectrum of the (charge reduced) complexes can be obtained by plotting the dissociation yield as a function of IR laser frequency. Experimental spectra are compared with theoretical spectra computed at the density functional theory (DFT) level to obtain detailed structural information of the complexes undergoing charge reduction, eventually providing new insights in their catalytic capabilities.
Publisher
International Symposium on Molecular Spectroscopy
Type of Resource
text
Genre of Resource
Conference Paper / Presentation
Language
eng
Permalink
http://hdl.handle.net/2142/100708
DOI
10.15278/isms.2018.WI03
Copyright and License Information
Copyright 2018 Musleh Uddin Munshi

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Abstracts & Presentations - 2018 International Symposium on Molecular Spectroscopy PRIMARY