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Title: Molecular spin frustration in mixed-chelate Fe5 and Fe6 oxo clusters with high ground state spin values

Abstract

The synthesis, structures, and magnetic properties are reported of three new polynuclear FeIII complexes containing the anions of picolinic acid (picH) and triethanolamine (teaH3) as chelates. The complexes [Fe6O2(OH)2(O2CR)4(pic)4(teaH)2] (R = Me (1), Ph (2)) and [Fe5O2(O2CBut)4(pic)3(teaH)2] (3) were obtained from the reaction of [Fe3O(O2CR)6(H2O)3](NO3) (R = Me, Ph, But) with picH and teaH3 in a 1:2:1 ratio in MeCN. The core of 1 and 2 consists of an [Fe43-O)2]8+ ‘planar-butterfly’ unit to which is attached an Fe atom on either side by bridging O atoms. The core of 3 consists of an [Fe53-O)2]11+ unit comprising two near-perpendicular vertex-sharing [Fe33-O)]7+ triangular units. Variable-temperature (T) and -field (H) solid-state dc and ac magnetization (M) studies in the 5.0–300 K temperature range revealed that 1 and 2 have an S = 5 ground state spin whereas 3 has an S = 5/2 ground state. Jij exchange couplings were calculated by DFT and a magnetostructural correlation (MSC) for polynuclear FeIII/O complexes. This allowed rationalization of the observed ground states from the analysis of the spin frustration effects operative, and provided good input values for fits of the experimental χMT vs T data to obtain the Jij values.

Authors:
 [1];  [2];  [1];  [2];  [1]
  1. Univ. of Florida, Gainesville, FL (United States)
  2. Central Michigan Univ., Mount Pleasant, MI (United States)
Publication Date:
Research Org.:
Central Michigan Univ., Mount Pleasant, MI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1601986
Alternate Identifier(s):
OSTI ID: 1702668
Grant/Contract Number:  
SC0018331
Resource Type:
Accepted Manuscript
Journal Name:
Polyhedron
Additional Journal Information:
Journal Volume: 176; Journal Issue: C; Journal ID: ISSN 0277-5387
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Iron; Cluster; Crystal structure; Magnetic properties; DFT

Citation Formats

Singh, Alok P., Joshi, Rajendra P., Abboud, Khalil A., Peralta, Juan E., and Christou, George. Molecular spin frustration in mixed-chelate Fe5 and Fe6 oxo clusters with high ground state spin values. United States: N. p., 2019. Web. doi:10.1016/j.poly.2019.114182.
Singh, Alok P., Joshi, Rajendra P., Abboud, Khalil A., Peralta, Juan E., & Christou, George. Molecular spin frustration in mixed-chelate Fe5 and Fe6 oxo clusters with high ground state spin values. United States. https://doi.org/10.1016/j.poly.2019.114182
Singh, Alok P., Joshi, Rajendra P., Abboud, Khalil A., Peralta, Juan E., and Christou, George. Wed . "Molecular spin frustration in mixed-chelate Fe5 and Fe6 oxo clusters with high ground state spin values". United States. https://doi.org/10.1016/j.poly.2019.114182. https://www.osti.gov/servlets/purl/1601986.
@article{osti_1601986,
title = {Molecular spin frustration in mixed-chelate Fe5 and Fe6 oxo clusters with high ground state spin values},
author = {Singh, Alok P. and Joshi, Rajendra P. and Abboud, Khalil A. and Peralta, Juan E. and Christou, George},
abstractNote = {The synthesis, structures, and magnetic properties are reported of three new polynuclear FeIII complexes containing the anions of picolinic acid (picH) and triethanolamine (teaH3) as chelates. The complexes [Fe6O2(OH)2(O2CR)4(pic)4(teaH)2] (R = Me (1), Ph (2)) and [Fe5O2(O2CBut)4(pic)3(teaH)2] (3) were obtained from the reaction of [Fe3O(O2CR)6(H2O)3](NO3) (R = Me, Ph, But) with picH and teaH3 in a 1:2:1 ratio in MeCN. The core of 1 and 2 consists of an [Fe4(µ3-O)2]8+ ‘planar-butterfly’ unit to which is attached an Fe atom on either side by bridging O atoms. The core of 3 consists of an [Fe5(µ3-O)2]11+ unit comprising two near-perpendicular vertex-sharing [Fe3(µ3-O)]7+ triangular units. Variable-temperature (T) and -field (H) solid-state dc and ac magnetization (M) studies in the 5.0–300 K temperature range revealed that 1 and 2 have an S = 5 ground state spin whereas 3 has an S = 5/2 ground state. Jij exchange couplings were calculated by DFT and a magnetostructural correlation (MSC) for polynuclear FeIII/O complexes. This allowed rationalization of the observed ground states from the analysis of the spin frustration effects operative, and provided good input values for fits of the experimental χMT vs T data to obtain the Jij values.},
doi = {10.1016/j.poly.2019.114182},
journal = {Polyhedron},
number = C,
volume = 176,
place = {United States},
year = {2019},
month = {10}
}

Journal Article:

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Figures / Tables:

Table 1 Table 1: Crystallographic and structure refinement data for Complexes 1 and 3

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