Spin state solvomorphism in a series of rare S = 1 manganese(III) complexes
Abstract
We present that structural, magnetic and spectroscopic data of four complex salts, [Mn(napsal2323)]NTf2, 1,[Mn(napsal2323)]ClO4, 2, [Mn(napsal2323)]BF4, 3 and [Mn(napsal2323)]NO3, 4, of the [Mn(napsal2323)]+ complex cation indicate that the Mn3+ ion is stabilized in the rare S = 1 spin triplet form in this ligand sphere. Zero-field splitting values of D = +19.6 cm-1 and |E| = 2.02 cm-1 for complex 1 were obtained by High Field Electron Paramagnetic Resonance (HFEPR) measurements conducted over a range of frequencies. Structural and magnetic data also indicate that co-crystallization of complexes 2 and 3 with 0.5 equivalents of ethanol yields the high spin S = 2 forms of the perchlorate and tetrafluoroborate solvates [Mn(napsal2323)]ClO4·0.5(C2H5OH), 2·0.5EtOH and [Mn(napsal2323)]BF4·0.5(C2H5OH), 3·0.5EtOH.
- Authors:
-
[1];
[1];
[2];
[2];
[3];
[4];
[1]
- University College Dublin (UCD) (Ireland)
- Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
- University of Dublin, College Green (Ireland)
- Queen's Univ., Belfast, Northern Ireland (United Kingdom)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Magnetic Quantum Materials (M2QM); Univ. of Florida, Gainesville, FL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC); Science Foundation Ireland (SFI); Irish Research Council; National Science Foundation (NSF)
- OSTI Identifier:
- 1602978
- Alternate Identifier(s):
- OSTI ID: 1544903
- Grant/Contract Number:
- SC0019330; 12/IP/1703; GOIPG/2018/2510; GOIPG/2015/2713; GOIPD/2016/503; DMR-1644779
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Volume: 48; Journal Issue: 41; Journal ID: ISSN 1477-9226
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Barker, Andrew, Kelly, Conor T., Kühne, Irina A., Hill, Stephen, Krzystek, J., Wix, Paul, Esien, Kane, Felton, Solveig, Müller-Bunz, Helge, and Morgan, Grace G. Spin state solvomorphism in a series of rare S = 1 manganese(III) complexes. United States: N. p., 2019.
Web. doi:10.1039/c9dt02476j.
Barker, Andrew, Kelly, Conor T., Kühne, Irina A., Hill, Stephen, Krzystek, J., Wix, Paul, Esien, Kane, Felton, Solveig, Müller-Bunz, Helge, & Morgan, Grace G. Spin state solvomorphism in a series of rare S = 1 manganese(III) complexes. United States. https://doi.org/10.1039/c9dt02476j
Barker, Andrew, Kelly, Conor T., Kühne, Irina A., Hill, Stephen, Krzystek, J., Wix, Paul, Esien, Kane, Felton, Solveig, Müller-Bunz, Helge, and Morgan, Grace G. Wed .
"Spin state solvomorphism in a series of rare S = 1 manganese(III) complexes". United States. https://doi.org/10.1039/c9dt02476j. https://www.osti.gov/servlets/purl/1602978.
@article{osti_1602978,
title = {Spin state solvomorphism in a series of rare S = 1 manganese(III) complexes},
author = {Barker, Andrew and Kelly, Conor T. and Kühne, Irina A. and Hill, Stephen and Krzystek, J. and Wix, Paul and Esien, Kane and Felton, Solveig and Müller-Bunz, Helge and Morgan, Grace G.},
abstractNote = {We present that structural, magnetic and spectroscopic data of four complex salts, [Mn(napsal2323)]NTf2, 1,[Mn(napsal2323)]ClO4, 2, [Mn(napsal2323)]BF4, 3 and [Mn(napsal2323)]NO3, 4, of the [Mn(napsal2323)]+ complex cation indicate that the Mn3+ ion is stabilized in the rare S = 1 spin triplet form in this ligand sphere. Zero-field splitting values of D = +19.6 cm-1 and |E| = 2.02 cm-1 for complex 1 were obtained by High Field Electron Paramagnetic Resonance (HFEPR) measurements conducted over a range of frequencies. Structural and magnetic data also indicate that co-crystallization of complexes 2 and 3 with 0.5 equivalents of ethanol yields the high spin S = 2 forms of the perchlorate and tetrafluoroborate solvates [Mn(napsal2323)]ClO4·0.5(C2H5OH), 2·0.5EtOH and [Mn(napsal2323)]BF4·0.5(C2H5OH), 3·0.5EtOH.},
doi = {10.1039/c9dt02476j},
journal = {Dalton Transactions},
number = 41,
volume = 48,
place = {United States},
year = {Wed Jul 17 00:00:00 EDT 2019},
month = {Wed Jul 17 00:00:00 EDT 2019}
}
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Figures / Tables:
Table 1: High spin (HS), intermediate spin (IS) and low spin (LS) S values for d4–d7 configurations
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Works referencing / citing this record:
Structure–function correlations in mononuclear manganese( iii ) spin crossover systems with a big conjugated hexadentate Schiff-base ligand
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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.