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Title: Cryogenic and Temperature-Dependent Photoelectron Spectroscopy of Metal Complexes

Abstract

Negative ion photoelectron spectroscopy (NIPES) coupled with electrospray ionization (ESI) has been proved to be a powerful gas-phase spectroscopic tool for characterizing electronic structures and chemical bonding of a variety of cluster anions and corresponding neutral radicals involved in the condensed phase reactions and transformations. Since the acquisition of cryogenic and temperature-controlling capabilities, broader range of research scope has been covered. This review summarizes our recent investigations on metal complexes employing cryogenic ESI-NIPES that provide us essential information towards understanding complicated condensed phase reactions including hydrocarbon activations and electron transfer reactions, and afford us spectroscopic probe of highly reactive transient species and intimate redox pairs. Special attention has been drawn to connect gas phase photodetachment processes with solution phase redox reactions. Photodetachment of transition metal-EDTA complexes has been systematically investigated to model the sequential oxidation reactions of these species in solutions. The obtained gas phase electron affinity (EA) is compared with the solution redox potential (E1/2) and the metal ionization potential (IP) for several series of homologous metal complexes to emphasize their intrinsic correlations with deviations being largely modulated by different degrees of ligand participations.

Authors:
 [1];  [1]; ORCiD logo [1]
  1. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1605137
Report Number(s):
PNNL-SA-149791
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
International Reviews in Physical Chemistry
Additional Journal Information:
Journal Volume: 39; Journal Issue: 1
Country of Publication:
United States
Language:
English

Citation Formats

Yuan, Qinqin, Cao, Wenjin, and Wang, Xue-Bin. Cryogenic and Temperature-Dependent Photoelectron Spectroscopy of Metal Complexes. United States: N. p., 2020. Web. doi:10.1080/0144235X.2020.1719699.
Yuan, Qinqin, Cao, Wenjin, & Wang, Xue-Bin. Cryogenic and Temperature-Dependent Photoelectron Spectroscopy of Metal Complexes. United States. doi:10.1080/0144235X.2020.1719699.
Yuan, Qinqin, Cao, Wenjin, and Wang, Xue-Bin. Fri . "Cryogenic and Temperature-Dependent Photoelectron Spectroscopy of Metal Complexes". United States. doi:10.1080/0144235X.2020.1719699.
@article{osti_1605137,
title = {Cryogenic and Temperature-Dependent Photoelectron Spectroscopy of Metal Complexes},
author = {Yuan, Qinqin and Cao, Wenjin and Wang, Xue-Bin},
abstractNote = {Negative ion photoelectron spectroscopy (NIPES) coupled with electrospray ionization (ESI) has been proved to be a powerful gas-phase spectroscopic tool for characterizing electronic structures and chemical bonding of a variety of cluster anions and corresponding neutral radicals involved in the condensed phase reactions and transformations. Since the acquisition of cryogenic and temperature-controlling capabilities, broader range of research scope has been covered. This review summarizes our recent investigations on metal complexes employing cryogenic ESI-NIPES that provide us essential information towards understanding complicated condensed phase reactions including hydrocarbon activations and electron transfer reactions, and afford us spectroscopic probe of highly reactive transient species and intimate redox pairs. Special attention has been drawn to connect gas phase photodetachment processes with solution phase redox reactions. Photodetachment of transition metal-EDTA complexes has been systematically investigated to model the sequential oxidation reactions of these species in solutions. The obtained gas phase electron affinity (EA) is compared with the solution redox potential (E1/2) and the metal ionization potential (IP) for several series of homologous metal complexes to emphasize their intrinsic correlations with deviations being largely modulated by different degrees of ligand participations.},
doi = {10.1080/0144235X.2020.1719699},
journal = {International Reviews in Physical Chemistry},
number = 1,
volume = 39,
place = {United States},
year = {2020},
month = {2}
}

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Redox potentials and related thermodynamic parameters of (diaminopolycarboxylato)metal(III/II) redox couples
journal, September 1989

  • Ogino, Hiroshi; Nagata, Takako; Ogino, Kazuko
  • Inorganic Chemistry, Vol. 28, Issue 19
  • DOI: 10.1021/ic00318a009

Negative Ion Photoelectron Spectroscopy Reveals Remarkable Noninnocence of Ligands in Nickel Bis(dithiolene) Complexes [Ni(dddt) 2 ] and [Ni(edo) 2 ]
journal, April 2016

  • Liu, Xing; Hou, Gao-Lei; Wang, Xuefeng
  • The Journal of Physical Chemistry A, Vol. 120, Issue 18
  • DOI: 10.1021/acs.jpca.6b02711

Synthesis and properties of novel donor-type metal–dithiolene complexes based on 5,6-dihydro-1,4-dioxine-2,3-dithiol (edo) ligand
journal, January 2001

  • Watanabe, Eiji; Fujiwara, Masahiro; Yamaura, Jun-Ichi
  • Journal of Materials Chemistry, Vol. 11, Issue 9
  • DOI: 10.1039/b102000p

Properties of perhalogenated { closo -B 10 } and { closo -B 11 } multiply charged anions and a critical comparison with { closo -B 12 } in the gas and the condensed phase
journal, January 2019

  • Warneke, Jonas; Konieczka, Szymon Z.; Hou, Gao-Lei
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 11
  • DOI: 10.1039/C8CP05313H

Spectroscopic Characterization, Computational Investigation, and Comparisons of ECX (E = As, P, and N; X = S and O) Anions
journal, June 2017

  • Hou, Gao-Lei; Chen, Bo; Transue, Wesley J.
  • Journal of the American Chemical Society, Vol. 139, Issue 26
  • DOI: 10.1021/jacs.7b02984