Electrospray ionization photoelectron spectroscopy of cryogenic [EDTA center dot M(ii)](2-) complexes (M = Ca, V-Zn): electronic structures and intrinsic redox properties

doi:10.1039/c8fd00175h

	Electrospray ionization photoelectron spectroscopy of cryogenic [EDTA center dot M(ii)](2-) complexes (M = Ca, V-Zn): electronic structures and intrinsic redox properties
	Yuan, Qinqin 1,2,3; Kong, Xiang-Tao 3; Hou, Gao-Lei 2; Jiang, Ling 3; Wang, Xue-Bin 2
刊名	FARADAY DISCUSSIONS
	2019-07-01
卷号	217 页码:383-395
ISSN号	1359-6640
DOI	10.1039/c8fd00175h
通讯作者	Jiang, Ling(ljiang@dicp.ac.cn) ; Wang, Xue-Bin(xuebin.wang@pnnl.gov)
英文摘要	We report here a systematic photoelectron spectroscopy (PES) and theoretical study of divalent transition metal (TM) EDTA complexes [EDTA center dot TM(ii)](2-) (TM = V-Zn), along with the Ca(ii) species for comparison. Gaseous TM dianions (TM = Ca, Mn, Co, Ni, Cu and Zn) were successfully generated via electrospray ionization, and their PE spectra, with 157, 193, and 266 nm photons, were obtained at 20 K. The spectrum of each TM complex shows an extra peak at the lowest electron binding energy (eBE), compared to that of [EDTA center dot Ca(ii)](2-). DFT calculations indicate a hexacoordinated metal-EDTA binding motif for all complexes, from which the vertical detachment energies (VDEs) are calculated and these agree well with the experimental values. The calculations further predict negative or very small VDEs for TM(ii) = V, Cr, and Fe, providing a rational explanation for why these three dianionic species are not observed in the gas phase. Direct spectral comparison, electron spin density differences, and MO analyses indicate that the least bound electrons are derived from TM d electrons with appreciable ligand contributions, in contrast to [EDTA center dot Ca(ii)](2-), in which the detachment is entirely derived from the ligand. The extent of ligand modulation, i.e. non-innocence of EDTA ligands in the oxidation process, is found to vary across the 3(rd) row of TMs. Comparing the gas-phase VDEs of [EDTA center dot TM(ii)](2-) with the 3(rd) ionization potentials of TMs and solution phase oxidation potentials reveals intrinsic correlations among these three quantities, with deviations being largely modulated by the ligand participation. The detailed microscopic information about the intrinsic electronic structures and bonding motifs of these complexes obtained in this work will help better understand the rich redox chemistries of these ubiquitous species under diverse environments. The present work, along with our previous studies, indicates that PES coupled with electrospray ionization is a unique ion spectroscopic tool that not only provides intrinsic electronic structure and bonding information about redox species, but also can predict the related electron transfer chemistries with quantitative capability.
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 at Pacific Northwest National Laboratory ; National Natural Science Foundation of China[21688102] ; Strategic Priority Research Program of the Chinese Academy of Sciences[XDB17000000]
WOS关键词	ETHYLENEDIAMINETETRAACETIC ACID COMPLEXES ; TRANSITION-METAL-COMPLEXES ; EDTA COMPLEXES ; INFRARED-SPECTRA ; CHARGED ANIONS ; ACETIC ACID ; CLUSTERS ; DNA ; PHOTODETACHMENT ; POTENTIALS
WOS研究方向	Chemistry
语种	英语
出版者	ROYAL SOC CHEMISTRY
WOS记录号	WOS:000476809000019
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 at Pacific Northwest National Laboratory ; DOE's Office of Biological and Environmental Research at Pacific Northwest National Laboratory ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Strategic Priority Research Program of the Chinese Academy of Sciences ; Strategic Priority Research Program of the Chinese Academy of Sciences ; 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 at Pacific Northwest National Laboratory ; DOE's Office of Biological and Environmental Research at Pacific Northwest National Laboratory ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Strategic Priority Research Program of the Chinese Academy of Sciences ; Strategic Priority Research Program of the Chinese Academy of Sciences ; 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 at Pacific Northwest National Laboratory ; DOE's Office of Biological and Environmental Research at Pacific Northwest National Laboratory ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Strategic Priority Research Program of the Chinese Academy of Sciences ; Strategic Priority Research Program of the Chinese Academy of Sciences ; 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 at Pacific Northwest National Laboratory ; DOE's Office of Biological and Environmental Research at Pacific Northwest National Laboratory ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Strategic Priority Research Program of the Chinese Academy of Sciences ; Strategic Priority Research Program of the Chinese Academy of Sciences
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/173698]
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	Jiang, Ling; Wang, Xue-Bin
作者单位	1.Univ Chinese Acad Sci, 19A Yuquan Rd, Beijing 100049, Peoples R China 2.Pacific Northwest Natl Lab, Phys Sci Div, 902 Battelle Blvd,POB 999,MS K8-88, Richland, WA 99352 USA 3.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, 457 Zhongshan Rd, Dalian 116023, Peoples R China
推荐引用方式 GB/T 7714	Yuan, Qinqin,Kong, Xiang-Tao,Hou, Gao-Lei,et al. Electrospray ionization photoelectron spectroscopy of cryogenic [EDTA center dot M(ii)](2-) complexes (M = Ca, V-Zn): electronic structures and intrinsic redox properties[J]. FARADAY DISCUSSIONS,2019,217:383-395.
APA	Yuan, Qinqin,Kong, Xiang-Tao,Hou, Gao-Lei,Jiang, Ling,&Wang, Xue-Bin.(2019).Electrospray ionization photoelectron spectroscopy of cryogenic [EDTA center dot M(ii)](2-) complexes (M = Ca, V-Zn): electronic structures and intrinsic redox properties.FARADAY DISCUSSIONS,217,383-395.
MLA	Yuan, Qinqin,et al."Electrospray ionization photoelectron spectroscopy of cryogenic [EDTA center dot M(ii)](2-) complexes (M = Ca, V-Zn): electronic structures and intrinsic redox properties".FARADAY DISCUSSIONS 217(2019):383-395.