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Title: Position Assignment and Oxidation State Recognition of Fe and Co Centers in Heterometallic Mixed-Valent Molecular Precursors for the Low-Temperature Preparation of Target Spinel Oxide Materials

Abstract

A series of mixed-valent, heterometallic (mixed-transition metal) diketonates that can be utilized as prospective volatile single-source precursors for the low-temperature preparation of M xM' 3–xO 4 spinel oxide materials is reported. Three iron–cobalt complexes with Fe/Co ratios of 1:1, 1:2, and 2:1 were synthesized by several methods using both solid-state and solution reactions. On the basis of nearly quantitative reaction yields, elemental analyses, and comparison of metal–oxygen bonds with those in homometallic analogues, heterometallic compounds were formulated as [Fe III(acac) 3][Co II(hfac) 2] (1), [Co II(hfac) 2][Fe III(acac) 3][Co II(hfac) 2] (2), and [Fe II(hfac) 2][Fe III(acac) 3][Co II(hfac) 2] (3). In the above heteroleptic complexes, the Lewis acidic, coordinatively unsaturated CoII/FeII centers chelated by two hexafluoroacetylacetonate (hfac) ligands maintain bridging interactions with oxygen atoms of acetylacetonate (acac) groups that chelate the neighboring Fe III metal ion. Preliminary assignment of Fe and Co positions/oxidation states in 1–3 drawn from X-ray structural investigation was corroborated by a number of complementary techniques. Single-crystal resonant synchrotron diffraction and neutron diffraction experiments unambiguously confirmed the location of Fe and Co sites in the molecules of dinuclear (1) and trinuclear (2) complexes, respectively. Direct analysis in real time mass spectrometry revealed the presence of Femore » III- and Co II-based fragments in the gas phase upon evaporation of precursors 1 and 2 as well as of Fe III, Fe II, and Co II species for complex 3. Theoretical investigation of two possible “valent isomers”, [Fe III(acac) 3][Co II(hfac) 2] (1) and [Co III(acac) 3][Fe II(hfac) 2] (1'), provided an additional support for the metal site/oxidation state assignment giving a preference of 6.48 kcal/mol for the experimentally observed molecule 1. Magnetic susceptibility measurements data are in agreement with the presence of high-spin FeIII and CoII magnetic centers with weak anti-ferromagnetic coupling between those in molecules of 1 and 2. Highly volatile heterometallic complexes 1–3 were found to act as effective single-source precursors for the low-temperature preparation of iron–cobalt spinel oxides Fe xCo 3–xO 4 known as important materials for diverse energy-related applications.« less

Authors:
 [1];  [1];  [1];  [2];  [3];  [4];  [5];  [6];  [7]; ORCiD logo [1]
  1. Department of Chemistry, University at Albany, Albany, New York 12222, United States
  2. Department of Chemistry, Illinois Institute of Technology, Chicago, Illinois 60616, United States
  3. Chemical and Engineering Materials Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
  4. CNRS, CRPP, UPR 8641, F-33600 Pessac, France; Univ. Bordeaux, UPR 8641, F-33600 Pessac, France; MOE Key Lab of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, P. R. China
  5. CNRS, CRPP, UPR 8641, F-33600 Pessac, France; Univ. Bordeaux, UPR 8641, F-33600 Pessac, France
  6. ChemMatCARS, Center for Advanced Radiation Sources, The University of Chicago, Argonne, Illinois 60439, United States
  7. Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, United States
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
NSFUNIVERSITYFOREIGN
OSTI Identifier:
1379425
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 56; Journal Issue: 16
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lieberman, Craig M., Barry, Matthew C., Wei, Zheng, Rogachev, Andrey Yu., Wang, Xiaoping, Liu, Jun-Liang, Clérac, Rodolphe, Chen, Yu-Sheng, Filatov, Alexander S., and Dikarev, Evgeny V.. Position Assignment and Oxidation State Recognition of Fe and Co Centers in Heterometallic Mixed-Valent Molecular Precursors for the Low-Temperature Preparation of Target Spinel Oxide Materials. United States: N. p., 2017. Web. doi:10.1021/acs.inorgchem.7b01032.
Lieberman, Craig M., Barry, Matthew C., Wei, Zheng, Rogachev, Andrey Yu., Wang, Xiaoping, Liu, Jun-Liang, Clérac, Rodolphe, Chen, Yu-Sheng, Filatov, Alexander S., & Dikarev, Evgeny V.. Position Assignment and Oxidation State Recognition of Fe and Co Centers in Heterometallic Mixed-Valent Molecular Precursors for the Low-Temperature Preparation of Target Spinel Oxide Materials. United States. doi:10.1021/acs.inorgchem.7b01032.
Lieberman, Craig M., Barry, Matthew C., Wei, Zheng, Rogachev, Andrey Yu., Wang, Xiaoping, Liu, Jun-Liang, Clérac, Rodolphe, Chen, Yu-Sheng, Filatov, Alexander S., and Dikarev, Evgeny V.. 2017. "Position Assignment and Oxidation State Recognition of Fe and Co Centers in Heterometallic Mixed-Valent Molecular Precursors for the Low-Temperature Preparation of Target Spinel Oxide Materials". United States. doi:10.1021/acs.inorgchem.7b01032.
@article{osti_1379425,
title = {Position Assignment and Oxidation State Recognition of Fe and Co Centers in Heterometallic Mixed-Valent Molecular Precursors for the Low-Temperature Preparation of Target Spinel Oxide Materials},
author = {Lieberman, Craig M. and Barry, Matthew C. and Wei, Zheng and Rogachev, Andrey Yu. and Wang, Xiaoping and Liu, Jun-Liang and Clérac, Rodolphe and Chen, Yu-Sheng and Filatov, Alexander S. and Dikarev, Evgeny V.},
abstractNote = {A series of mixed-valent, heterometallic (mixed-transition metal) diketonates that can be utilized as prospective volatile single-source precursors for the low-temperature preparation of MxM'3–xO4 spinel oxide materials is reported. Three iron–cobalt complexes with Fe/Co ratios of 1:1, 1:2, and 2:1 were synthesized by several methods using both solid-state and solution reactions. On the basis of nearly quantitative reaction yields, elemental analyses, and comparison of metal–oxygen bonds with those in homometallic analogues, heterometallic compounds were formulated as [FeIII(acac)3][CoII(hfac)2] (1), [CoII(hfac)2][FeIII(acac)3][CoII(hfac)2] (2), and [FeII(hfac)2][FeIII(acac)3][CoII(hfac)2] (3). In the above heteroleptic complexes, the Lewis acidic, coordinatively unsaturated CoII/FeII centers chelated by two hexafluoroacetylacetonate (hfac) ligands maintain bridging interactions with oxygen atoms of acetylacetonate (acac) groups that chelate the neighboring FeIII metal ion. Preliminary assignment of Fe and Co positions/oxidation states in 1–3 drawn from X-ray structural investigation was corroborated by a number of complementary techniques. Single-crystal resonant synchrotron diffraction and neutron diffraction experiments unambiguously confirmed the location of Fe and Co sites in the molecules of dinuclear (1) and trinuclear (2) complexes, respectively. Direct analysis in real time mass spectrometry revealed the presence of FeIII- and CoII-based fragments in the gas phase upon evaporation of precursors 1 and 2 as well as of FeIII, FeII, and CoII species for complex 3. Theoretical investigation of two possible “valent isomers”, [FeIII(acac)3][CoII(hfac)2] (1) and [CoIII(acac)3][FeII(hfac)2] (1'), provided an additional support for the metal site/oxidation state assignment giving a preference of 6.48 kcal/mol for the experimentally observed molecule 1. Magnetic susceptibility measurements data are in agreement with the presence of high-spin FeIII and CoII magnetic centers with weak anti-ferromagnetic coupling between those in molecules of 1 and 2. Highly volatile heterometallic complexes 1–3 were found to act as effective single-source precursors for the low-temperature preparation of iron–cobalt spinel oxides FexCo3–xO4 known as important materials for diverse energy-related applications.},
doi = {10.1021/acs.inorgchem.7b01032},
journal = {Inorganic Chemistry},
number = 16,
volume = 56,
place = {United States},
year = 2017,
month = 7
}
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