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Title: Photoelectron spectroscopic and computational study of [EDTA•M(III)]- complexes (M = H3, Al, Sc, V-Co)

Abstract

Metal-EDTA complexes are commonly existed as biological redox reagents. We havegenerated a series of such complexes, [EDTA•M(III)]- (M = Al, Sc, V-Co), via electrospray ionization and characterized them by cryogenic mass-selected negative ion photoelectron spectroscopy (NIPES) and theoretical calculations. Experiments clearly revealed one more spectral band at low electron binding energy for transition metal complexes with d electrons (M = V-Co) than those without d electrons (M = Al and Sc). Quantum chemical calculations suggested that all of the metal-complexes possess hexacoordinated metal-ligand binding motifs, from which the calculated adiabatic/vertical detachment energy (ADE/VDE) and band gaps are in good agreement with experimental values. Direct spectrum and electronic structure analyses indicted that [EDTA•V(III)]- can be easily oxidized to [EDTA•V(IV)] with the smallest ADE/VDE of 3.95/4.40 eV among these metal-complexes, but further oxidation is hindered by the existence of a 2.30 eV band gap, a fact that accords with the special redox behavior of vanadium-containing species in biology cells. Spin density and molecular orbital analyses reveal that [EDTA•V(III)]- was overwhelmingly detached from vanadium atom, in a stark contrast to [EDTA•Sc(III)/Al(III)]- where the detachment occurred from the EDTA ligand. For all other metal complex anions, from M = Cr to Co, the detachmentmore » process is derived from contributions from both the metal and ligand. The intrinsic electronic and geometric structures of these complexes, obtained in this work, provide a molecular foundation to better understand their redox chemistries and specific metal bindings in condensed phases and biology cells.« less

Authors:
 [1];  [2]; ORCiD logo [3];  [2]; ORCiD logo [3]
  1. UNIVERSITY PROGRAMS
  2. Chinese Academy of Sciences
  3. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1601787
Report Number(s):
PNNL-SA-132912
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 20; Journal Issue: 29
Country of Publication:
United States
Language:
English

Citation Formats

Yuan, Qinqin, Kong, Xiang-Tao, Hou, Gaolei, Jiang, Ling, and Wang, Xue-Bin. Photoelectron spectroscopic and computational study of [EDTA•M(III)]- complexes (M = H3, Al, Sc, V-Co). United States: N. p., 2018. Web. doi:10.1039/c8cp01548a.
Yuan, Qinqin, Kong, Xiang-Tao, Hou, Gaolei, Jiang, Ling, & Wang, Xue-Bin. Photoelectron spectroscopic and computational study of [EDTA•M(III)]- complexes (M = H3, Al, Sc, V-Co). United States. doi:10.1039/c8cp01548a.
Yuan, Qinqin, Kong, Xiang-Tao, Hou, Gaolei, Jiang, Ling, and Wang, Xue-Bin. Tue . "Photoelectron spectroscopic and computational study of [EDTA•M(III)]- complexes (M = H3, Al, Sc, V-Co)". United States. doi:10.1039/c8cp01548a.
@article{osti_1601787,
title = {Photoelectron spectroscopic and computational study of [EDTA•M(III)]- complexes (M = H3, Al, Sc, V-Co)},
author = {Yuan, Qinqin and Kong, Xiang-Tao and Hou, Gaolei and Jiang, Ling and Wang, Xue-Bin},
abstractNote = {Metal-EDTA complexes are commonly existed as biological redox reagents. We havegenerated a series of such complexes, [EDTA•M(III)]- (M = Al, Sc, V-Co), via electrospray ionization and characterized them by cryogenic mass-selected negative ion photoelectron spectroscopy (NIPES) and theoretical calculations. Experiments clearly revealed one more spectral band at low electron binding energy for transition metal complexes with d electrons (M = V-Co) than those without d electrons (M = Al and Sc). Quantum chemical calculations suggested that all of the metal-complexes possess hexacoordinated metal-ligand binding motifs, from which the calculated adiabatic/vertical detachment energy (ADE/VDE) and band gaps are in good agreement with experimental values. Direct spectrum and electronic structure analyses indicted that [EDTA•V(III)]- can be easily oxidized to [EDTA•V(IV)] with the smallest ADE/VDE of 3.95/4.40 eV among these metal-complexes, but further oxidation is hindered by the existence of a 2.30 eV band gap, a fact that accords with the special redox behavior of vanadium-containing species in biology cells. Spin density and molecular orbital analyses reveal that [EDTA•V(III)]- was overwhelmingly detached from vanadium atom, in a stark contrast to [EDTA•Sc(III)/Al(III)]- where the detachment occurred from the EDTA ligand. For all other metal complex anions, from M = Cr to Co, the detachment process is derived from contributions from both the metal and ligand. The intrinsic electronic and geometric structures of these complexes, obtained in this work, provide a molecular foundation to better understand their redox chemistries and specific metal bindings in condensed phases and biology cells.},
doi = {10.1039/c8cp01548a},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 29,
volume = 20,
place = {United States},
year = {2018},
month = {8}
}

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