Magnetic Exchange Interaction in Nitronyl Nitroxide Radical-Based Single Crystals of 3d Metal Complexes: A Combined Experimental and Theoretical Study
- Publication type:
- Journal article
- Metadata:
-
- Autoren
- Pramod Bhatt
- Kubandiran Kolanji
- Anela Ivanova
- Arvind Yogi
- Gerhard Jakob
- Mayuresh D Mukadam
- Seikh Mohammad Yusuf
- Martin Baumgarten
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000427939400050&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.1021/acsomega.7b01669
- Externe Identifier
- Clarivate Analytics Document Solution ID: FZ9NT
- PubMed Identifier: 31458563
- ISSN
- 2470-1343
- Ausgabe der Veröffentlichung
- 3
- Zeitschrift
- ACS OMEGA
- Paginierung
- 2918 - 2933
- Datum der Veröffentlichung
- 2018
- Status
- Published
- Titel
- Magnetic Exchange Interaction in Nitronyl Nitroxide Radical-Based Single Crystals of 3d Metal Complexes: A Combined Experimental and Theoretical Study
- Sub types
- Article
- Ausgabe der Zeitschrift
- 3
Data source: Web of Science (Lite)
- Other metadata sources:
-
- Autoren
- Pramod Bhatt
- Kubandiran Kolanji
- Anela Ivanova
- Arvind Yogi
- Gerhard Jakob
- Mayuresh D Mukadam
- Seikh Mohammad Yusuf
- Martin Baumgarten
- DOI
- 10.1021/acsomega.7b01669
- eISSN
- 2470-1343
- ISSN
- 2470-1343
- Ausgabe der Veröffentlichung
- 3
- Zeitschrift
- ACS Omega
- Sprache
- en
- Online publication date
- 2018
- Paginierung
- 2918 - 2933
- Datum der Veröffentlichung
- 2018
- Status
- Published
- Herausgeber
- American Chemical Society (ACS)
- Herausgeber URL
- http://dx.doi.org/10.1021/acsomega.7b01669
- Datum der Datenerfassung
- 2023
- Titel
- Magnetic Exchange Interaction in Nitronyl Nitroxide Radical-Based Single Crystals of 3d Metal Complexes: A Combined Experimental and Theoretical Study
- Ausgabe der Zeitschrift
- 3
Data source: Crossref
- Abstract
- Two stable nitronyl nitroxide free radicals {<b>R</b> <sup><b>1</b></sup> = 4'-methoxy-phenyl-4,4,5,5,-tetramethylimidazoline-1-oxyl-3-oxide (NNPhOMe) and <b>R</b> <sup><b>2</b></sup> = 2-(2'-thienyl)-4,4,5,5-tetramethylimidazoline 3-oxide 1-oxyl (NNT)} are successfully synthesized using Ullmann condensation. The reactions of these two radicals with 3d transition metal ions, in the form of M(hfac)<sub>2</sub> (where M = Co or Mn, hfac: hexafluoroacetylacetone), result in four metal-organic complexes Co(hfac)<sub>2</sub>(NNPhOMe)<sub>2</sub>, <b>1</b>; Co(hfac)<sub>2</sub>(NNT)<sub>2</sub>·(H<sub>2</sub>O), <b>2</b>; Mn(hfac)<sub>2</sub>(NNPhOMe)·<i>x</i>(C<sub>7</sub>H<sub>16</sub>), <b>3</b>; and Mn(hfac)<sub>2</sub>(NNT)<sub>2</sub>, <b>4</b>. The crystal structure and magnetic properties of these complexes are investigated by single-crystal X-ray diffraction, dc magnetization, infrared, and electron paramagnetic resonance spectroscopies. The compounds <b>1</b> and <b>4</b> crystallize in the triclinic, <i>P</i>1̅, space group, whereas complex <b>3</b> crystallizes in the monoclinic structure with the <i>C</i>2/<i>c</i> space group and forms chain-like structure along the <i>c</i> direction. The complex <b>2</b> crystallizes in the monoclinic symmetry with the <i>P</i>2<sub>1</sub>/<i>c</i> space group in which the N-O unit of the radical coordinates with the Co ion through hydrogen bonding of a water molecule. All compounds exhibit antiferromagnetic interactions between the transition metal ions and nitronyl nitroxide radicals. The magnetic exchange interactions (<i>J</i>/<i>K</i> <sub>B</sub>) are derived using isotropic spin Hamiltonian <i>H</i> = -2<i>J</i>∑(<i>S</i> <sub>metal</sub> <i>S</i> <sub>radical</sub>) for the model fitting to the magnetic susceptibility data for <b>1</b>, <b>2</b>, <b>3</b>, and <b>4</b>. The exchange interaction strengths are found to be -328, -1.25, -248, and -256 K, for the <b>1</b>, <b>2</b>, <b>3</b>, and <b>4</b> metal-organic complexes, respectively. Quantum chemical density functional theory (DFT) computations are carried out on several models of the metal-radical complexes to elucidate the magnetic interactions at the molecular level. The calculations show that a small part of the inorganic spins are delocalized over the oxygens from hfac {∼0.03 for Co(II) and ∼0.015 for Mn(II)}, whereas a more significant fraction {∼0.24 for Mn(II) and ∼0.13 for Co(II)} of delocalized spins from the metal ion is transferred to the coordinated oxygen atom(s) of nitronyl nitroxide.
- Addresses
- Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085, India.
- Autoren
- Pramod Bhatt
- Kubandiran Kolanji
- Anela Ivanova
- Arvind Yogi
- Gerhard Jakob
- Mayuresh D Mukadam
- Seikh Mohammad Yusuf
- Martin Baumgarten
- DOI
- 10.1021/acsomega.7b01669
- eISSN
- 2470-1343
- Externe Identifier
- PubMed Identifier: 31458563
- PubMed Central ID: PMC6641457
- Funding acknowledgements
- Deutsche Forschungsgemeinschaft: SFB-TR49
- Open access
- true
- ISSN
- 2470-1343
- Ausgabe der Veröffentlichung
- 3
- Zeitschrift
- ACS omega
- Sprache
- eng
- Medium
- Electronic-eCollection
- Online publication date
- 2018
- Open access status
- Open Access
- Paginierung
- 2918 - 2933
- Datum der Veröffentlichung
- 2018
- Status
- Published
- Datum der Datenerfassung
- 2019
- Titel
- Magnetic Exchange Interaction in Nitronyl Nitroxide Radical-Based Single Crystals of 3d Metal Complexes: A Combined Experimental and Theoretical Study.
- Sub types
- research-article
- Journal Article
- Ausgabe der Zeitschrift
- 3
Files
https://pubs.acs.org/doi/pdf/10.1021/acsomega.7b01669 https://europepmc.org/articles/PMC6641457?pdf=render
Data source: Europe PubMed Central
- Abstract
- Two stable nitronyl nitroxide free radicals {R 1 = 4'-methoxy-phenyl-4,4,5,5,-tetramethylimidazoline-1-oxyl-3-oxide (NNPhOMe) and R 2 = 2-(2'-thienyl)-4,4,5,5-tetramethylimidazoline 3-oxide 1-oxyl (NNT)} are successfully synthesized using Ullmann condensation. The reactions of these two radicals with 3d transition metal ions, in the form of M(hfac)2 (where M = Co or Mn, hfac: hexafluoroacetylacetone), result in four metal-organic complexes Co(hfac)2(NNPhOMe)2, 1; Co(hfac)2(NNT)2·(H2O), 2; Mn(hfac)2(NNPhOMe)·x(C7H16), 3; and Mn(hfac)2(NNT)2, 4. The crystal structure and magnetic properties of these complexes are investigated by single-crystal X-ray diffraction, dc magnetization, infrared, and electron paramagnetic resonance spectroscopies. The compounds 1 and 4 crystallize in the triclinic, P1̅, space group, whereas complex 3 crystallizes in the monoclinic structure with the C2/c space group and forms chain-like structure along the c direction. The complex 2 crystallizes in the monoclinic symmetry with the P21/c space group in which the N-O unit of the radical coordinates with the Co ion through hydrogen bonding of a water molecule. All compounds exhibit antiferromagnetic interactions between the transition metal ions and nitronyl nitroxide radicals. The magnetic exchange interactions (J/K B) are derived using isotropic spin Hamiltonian H = -2J∑(S metal S radical) for the model fitting to the magnetic susceptibility data for 1, 2, 3, and 4. The exchange interaction strengths are found to be -328, -1.25, -248, and -256 K, for the 1, 2, 3, and 4 metal-organic complexes, respectively. Quantum chemical density functional theory (DFT) computations are carried out on several models of the metal-radical complexes to elucidate the magnetic interactions at the molecular level. The calculations show that a small part of the inorganic spins are delocalized over the oxygens from hfac {∼0.03 for Co(II) and ∼0.015 for Mn(II)}, whereas a more significant fraction {∼0.24 for Mn(II) and ∼0.13 for Co(II)} of delocalized spins from the metal ion is transferred to the coordinated oxygen atom(s) of nitronyl nitroxide.
- Date of acceptance
- 2018
- Autoren
- Pramod Bhatt
- Kubandiran Kolanji
- Anela Ivanova
- Arvind Yogi
- Gerhard Jakob
- Mayuresh D Mukadam
- Seikh Mohammad Yusuf
- Martin Baumgarten
- Autoren-URL
- https://www.ncbi.nlm.nih.gov/pubmed/31458563
- DOI
- 10.1021/acsomega.7b01669
- eISSN
- 2470-1343
- Externe Identifier
- PubMed Central ID: PMC6641457
- Ausgabe der Veröffentlichung
- 3
- Zeitschrift
- ACS Omega
- Sprache
- eng
- Country
- United States
- Paginierung
- 2918 - 2933
- Datum der Veröffentlichung
- 2018
- Status
- Published online
- Titel
- Magnetic Exchange Interaction in Nitronyl Nitroxide Radical-Based Single Crystals of 3d Metal Complexes: A Combined Experimental and Theoretical Study.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 3
Data source: PubMed
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