Photoelectron spectroscopic and computational studies of [EDTA center dot M(III)](-) complexes (M = H-3, Al, Sc, V-Co)

doi:10.1039/c8cp01548a

	Photoelectron spectroscopic and computational studies of [EDTA center dot M(III)](-) complexes (M = H-3, Al, Sc, V-Co)
	Hou, Gao-Lei 3; Wang, Xue-Bin 3; Yuan, Qinqin 1,2,3; Kong, Xiang-Tao 2; Jiang, Ling 2
刊名	PHYSICAL CHEMISTRY CHEMICAL PHYSICS
	2018-08-07
卷号	20 期号:29 页码:19458-19469
ISSN号	1463-9076
DOI	10.1039/c8cp01548a
通讯作者	Jiang, Ling(ljiang@dicp.ac.cn) ; Wang, Xue-Bin(xuebin.wang@pnal.gov)
英文摘要	Metal-EDTA complexes commonly exist as biological redox reagents. We have generated a series of such complexes, [EDTA center dot M(III)](-) (M = Al, Sc, V-Co), via electrospray ionization and characterized them by cryogenic mass-selected negative ion photoelectron spectroscopy (NIPES) and quantum chemical computations. Experiments clearly revealed one more spectral band at low electron binding energy for transition metal complexes with d electrons (M = V-Co) compared to 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 center dot V(III)](-) can be easily oxidized to [EDTA center dot 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 biological cells. Spin density and molecular orbital analyses reveal that [EDTA center dot V(III)](-) was overwhelmingly detached from the vanadium atom, in stark contrast to [EDTA center dot 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 biological cells.
资助项目	U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences ; DOE's Office of Biological and Environmental Research ; National Natural Science Foundation of China[21688102] ; Strategic Priority Research Program of the Chinese Academy of Science[XDB17000000]
WOS关键词	METAL-EDTA COMPLEXES ; CYSTEINE METHYL-ESTER ; MOLECULAR-STRUCTURE ; HYDROGEN-PEROXIDE ; SPECTROPHOTOMETRIC DETERMINATION ; ELECTRONIC-STRUCTURE ; DENSITY FUNCTIONALS ; FE(III) COMPLEXES ; AQUEOUS-SOLUTIONS ; CRYSTAL-STRUCTURE
WOS研究方向	Chemistry ; Physics
语种	英语
出版者	ROYAL SOC CHEMISTRY
WOS记录号	WOS:000448132600020
资助机构	U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences ; U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences ; DOE's Office of Biological and Environmental Research ; DOE's Office of Biological and Environmental Research ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Strategic Priority Research Program of the Chinese Academy of Science ; Strategic Priority Research Program of the Chinese Academy of Science ; U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences ; U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences ; DOE's Office of Biological and Environmental Research ; DOE's Office of Biological and Environmental Research ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Strategic Priority Research Program of the Chinese Academy of Science ; Strategic Priority Research Program of the Chinese Academy of Science ; U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences ; U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences ; DOE's Office of Biological and Environmental Research ; DOE's Office of Biological and Environmental Research ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Strategic Priority Research Program of the Chinese Academy of Science ; Strategic Priority Research Program of the Chinese Academy of Science ; U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences ; U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences ; DOE's Office of Biological and Environmental Research ; DOE's Office of Biological and Environmental Research ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Strategic Priority Research Program of the Chinese Academy of Science ; Strategic Priority Research Program of the Chinese Academy of Science
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/166868]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
通讯作者	Wang, Xue-Bin; Jiang, Ling
作者单位	1.Univ Chinese Acad Sci, 19A Yuquan Rd, Beijing 100049, Peoples R China 2.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, 457 Zhongshan Rd, Dalian 116023, Peoples R China 3.Pacific Northwest Natl Lab, Phys Sci Div, 902 Battelle Blvd,POB 99-9,MS K8-88, Richland, WA 99352 USA
推荐引用方式 GB/T 7714	Hou, Gao-Lei,Wang, Xue-Bin,Yuan, Qinqin,et al. Photoelectron spectroscopic and computational studies of [EDTA center dot M(III)](-) complexes (M = H-3, Al, Sc, V-Co)[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2018,20(29):19458-19469.
APA	Hou, Gao-Lei,Wang, Xue-Bin,Yuan, Qinqin,Kong, Xiang-Tao,&Jiang, Ling.(2018).Photoelectron spectroscopic and computational studies of [EDTA center dot M(III)](-) complexes (M = H-3, Al, Sc, V-Co).PHYSICAL CHEMISTRY CHEMICAL PHYSICS,20(29),19458-19469.
MLA	Hou, Gao-Lei,et al."Photoelectron spectroscopic and computational studies of [EDTA center dot M(III)](-) complexes (M = H-3, Al, Sc, V-Co)".PHYSICAL CHEMISTRY CHEMICAL PHYSICS 20.29(2018):19458-19469.