Photoelectron spectroscopic and computational studies of [EDTA center dot M(III)](-) complexes (M = H-3, Al, Sc, V-Co)
文献类型：期刊论文
| 作者 | Hou, Gao-Lei3; Wang, Xue-Bin3; Yuan, Qinqin1,2,3; Kong, Xiang-Tao2; Jiang, Ling2 |
| 刊名 | PHYSICAL CHEMISTRY CHEMICAL PHYSICS
 |
| 出版日期 | 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. |
| 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 |
| 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研究方向 | Chemistry ; Physics |
| 语种 | 英语 |
| WOS记录号 | WOS:000448132600020 |
| 出版者 | ROYAL SOC CHEMISTRY |
| 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 |
| 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. |
入库方式： OAI收割
来源：大连化学物理研究所
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