Single Ion Anisotropy of CrIII and FeIII in a Series of {Ti7M} Rings

A series of heterometallic [Ti IV 7 M III ] rings are reported which contain a single paramagnetic metal centre, either Fe III or Cr III . The structures contain an octagon of metals bridged by oxides within the ring and pivalate ligands outside the ring. The structures encapsulate a single cation,...

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Vydáno v:	Applied magnetic resonance Ročník 51; číslo 11; s. 1251 - 1265
Hlavní autoři:	Kostopoulos, Andreas K., Timco, Grigore A., Tuna, Floriana, Vitórica-Yrezábal, Iñigo J., Whitehead, George F. S., Bamberger, Heiko, van Slageren, Joris, Collison, David, McInnes, Eric J. L., Winpenny, Richard E. P.
Médium:	Journal Article
Jazyk:	angličtina
Vydáno:	Vienna Springer Vienna 01.11.2020 Springer Nature B.V
Témata:	Acids Anisotropy Atoms and Molecules in Strong Fields Cations Cesium Dante Gatteschi: On the Occasion of His 75th Birthday Laser Matter Interaction Organic Chemistry Original Paper Physical Chemistry Physics Physics and Astronomy Radiation Sensors Single crystals Solid State Physics Solvents Spectroscopy/Spectrometry Spectrum analysis Titanium
ISSN:	0937-9347, 1613-7507
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Abstract	A series of heterometallic [Ti IV 7 M III ] rings are reported which contain a single paramagnetic metal centre, either Fe III or Cr III . The structures contain an octagon of metals bridged by oxides within the ring and pivalate ligands outside the ring. The structures encapsulate a single cation, either a secondary ammonium cation or a cesium. Multi-frequency EPR spectroscopy was used to measure the zero-field splitting parameters for the paramagnetic metal sites. The Fe III sites have rhombic anisotropy, with D around − 0.18 cm −1 and λ (= D/E ) approximately 0.25. The Cr III have a more axial anisotropy, with D around − 0.5 cm −1 and λ around 0.05. Attempts to find a magneto-structural correlation are vitiated by the difficulty of refining the challenging crystal structures.
AbstractList	A series of heterometallic [Ti IV 7 M III ] rings are reported which contain a single paramagnetic metal centre, either Fe III or Cr III . The structures contain an octagon of metals bridged by oxides within the ring and pivalate ligands outside the ring. The structures encapsulate a single cation, either a secondary ammonium cation or a cesium. Multi-frequency EPR spectroscopy was used to measure the zero-field splitting parameters for the paramagnetic metal sites. The Fe III sites have rhombic anisotropy, with D around − 0.18 cm −1 and λ (= D/E ) approximately 0.25. The Cr III have a more axial anisotropy, with D around − 0.5 cm −1 and λ around 0.05. Attempts to find a magneto-structural correlation are vitiated by the difficulty of refining the challenging crystal structures. A series of heterometallic [TiIV7MIII] rings are reported which contain a single paramagnetic metal centre, either FeIII or CrIII. The structures contain an octagon of metals bridged by oxides within the ring and pivalate ligands outside the ring. The structures encapsulate a single cation, either a secondary ammonium cation or a cesium. Multi-frequency EPR spectroscopy was used to measure the zero-field splitting parameters for the paramagnetic metal sites. The FeIII sites have rhombic anisotropy, with D around − 0.18 cm−1 and λ (= D/E) approximately 0.25. The CrIII have a more axial anisotropy, with D around − 0.5 cm−1 and λ around 0.05. Attempts to find a magneto-structural correlation are vitiated by the difficulty of refining the challenging crystal structures.
Author	Vitórica-Yrezábal, Iñigo J. Bamberger, Heiko van Slageren, Joris Kostopoulos, Andreas K. Timco, Grigore A. Whitehead, George F. S. Collison, David Tuna, Floriana McInnes, Eric J. L. Winpenny, Richard E. P.
Author_xml	– sequence: 1 givenname: Andreas K. surname: Kostopoulos fullname: Kostopoulos, Andreas K. organization: Department of Chemistry and Photon Science Institute, The University of Manchester – sequence: 2 givenname: Grigore A. surname: Timco fullname: Timco, Grigore A. organization: Department of Chemistry and Photon Science Institute, The University of Manchester – sequence: 3 givenname: Floriana surname: Tuna fullname: Tuna, Floriana organization: Department of Chemistry and Photon Science Institute, The University of Manchester – sequence: 4 givenname: Iñigo J. surname: Vitórica-Yrezábal fullname: Vitórica-Yrezábal, Iñigo J. organization: Department of Chemistry and Photon Science Institute, The University of Manchester – sequence: 5 givenname: George F. S. surname: Whitehead fullname: Whitehead, George F. S. organization: Department of Chemistry and Photon Science Institute, The University of Manchester – sequence: 6 givenname: Heiko surname: Bamberger fullname: Bamberger, Heiko organization: Institut Für Physikalische Chemie, Universität Stuttgart – sequence: 7 givenname: Joris surname: van Slageren fullname: van Slageren, Joris organization: Institut Für Physikalische Chemie, Universität Stuttgart – sequence: 8 givenname: David surname: Collison fullname: Collison, David organization: Department of Chemistry and Photon Science Institute, The University of Manchester – sequence: 9 givenname: Eric J. L. surname: McInnes fullname: McInnes, Eric J. L. organization: Department of Chemistry and Photon Science Institute, The University of Manchester – sequence: 10 givenname: Richard E. P. orcidid: 0000-0002-7101-3963 surname: Winpenny fullname: Winpenny, Richard E. P. email: richard.winpenny@manchester.ac.uk organization: Department of Chemistry and Photon Science Institute, The University of Manchester
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Cites_doi	10.1039/C7CP07443C 10.1002/chem.201604872 10.1002/anie.201706679 10.1021/acs.inorgchem.8b01764 10.1002/9783527690541 10.1107/S0021889808042726 10.1021/ic00227a003 10.1039/C2DT32478D 10.1002/anie.201502730 10.1039/C6CC05094H 10.1016/j.jmr.2005.08.013 10.1021/ar960157p 10.1021/ja9818755 10.1038/nphys2431 10.1021/jacs.5b11802 10.1002/chem.200801895 10.1021/acs.inorgchem.5b02429 10.1007/978-3-642-74599-7 10.1016/j.jinorgbio.2018.02.003 10.1002/1521-3765(20020104)8:1<277::AID-CHEM277>3.0.CO;2-D 10.1107/S2053229614024218 10.1021/ic00348a030 10.1039/c0cc01188f
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Snippet	A series of heterometallic [Ti IV 7 M III ] rings are reported which contain a single paramagnetic metal centre, either Fe III or Cr III . The structures... A series of heterometallic [TiIV7MIII] rings are reported which contain a single paramagnetic metal centre, either FeIII or CrIII. The structures contain an...
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SubjectTerms	Acids Anisotropy Atoms and Molecules in Strong Fields Cations Cesium Dante Gatteschi: On the Occasion of His 75th Birthday Laser Matter Interaction Organic Chemistry Original Paper Physical Chemistry Physics Physics and Astronomy Radiation Sensors Single crystals Solid State Physics Solvents Spectroscopy/Spectrometry Spectrum analysis Titanium
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Title	Single Ion Anisotropy of CrIII and FeIII in a Series of {Ti7M} Rings
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