Magnetic coupling of divalent metal centers in postsynthetic metal exchanged bimetallic DUT-49 MOFs by EPR spectroscopy
EPR measurements at X- (9.5 GHz), Q- (34 GHz) and W-band (94 GHz) on paddlewheel (PW) type post-synthetic metal exchanged DUT-49(M,M): M- Zn, Mn, Cu MOFs are here reported (DUT–Dresden University of Technology). Temperature-dependent X-band measurements are recorded from T = 7 K to T = 170 K on mono...
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| Format: | Article |
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AIP Publishing LLC
2023-01-01
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| Series: | AIP Advances |
| Online Access: | http://dx.doi.org/10.1063/9.0000532 |
| _version_ | 1811172629435908096 |
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| author | Kavipriya Thangavel Matthias Mendt Bikash Garai Andrea Folli Volodymyr Bon Damien M. Murphy Stefan Kaskel Andreas Pöppl |
| author_facet | Kavipriya Thangavel Matthias Mendt Bikash Garai Andrea Folli Volodymyr Bon Damien M. Murphy Stefan Kaskel Andreas Pöppl |
| author_sort | Kavipriya Thangavel |
| collection | DOAJ |
| description | EPR measurements at X- (9.5 GHz), Q- (34 GHz) and W-band (94 GHz) on paddlewheel (PW) type post-synthetic metal exchanged DUT-49(M,M): M- Zn, Mn, Cu MOFs are here reported (DUT–Dresden University of Technology). Temperature-dependent X-band measurements are recorded from T = 7 K to T = 170 K on monometallic DUT-49(Cu), DUT-49(Mn), and bimetallic DUT-49(Cu0.7Zn0.3), DUT-49(Cu0.5Mn0.5) MOFs. In the case of the CuII - CuII dimers in DUT-49(Cu), an isotropic exchange coupling of the metal ions (2J = −240(11) cm−1) determined from the EPR intensity of the S = 1 spin state of the CuII–CuII dimers using the Bleaney Blowers equation. The sign of the found isotropic exchange coupling constant confirms an antiferromagnetic coupling between the cupric ions. Also, the MnII ions in the paddle wheels of DUT-49(Mn) are antiferromagnetically coupled. However, at low temperatures, EPR measurements reveal the presence of CuII and MnII monomers in DUT-49(Cu) and DUT-49(Mn), respectively, either associated with extra framework sites or defective paddle wheels. Otherwise, EPR signals observed for bimetallic DUT-49(Cu0.7Zn0.3) and DUT-49(Cu0.5Mn0.5) MOFs reveal the formation of mixed ion CuII–ZnII and CuII–MnII paddle wheels with SCuZn =1/2 and SCuMn = 2 spin states, respectively. |
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| issn | 2158-3226 |
| language | English |
| last_indexed | 2024-04-10T17:33:23Z |
| publishDate | 2023-01-01 |
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| series | AIP Advances |
| spelling | doaj.art-4da0bfbc1255405cbd3a6829638486732023-02-03T16:42:06ZengAIP Publishing LLCAIP Advances2158-32262023-01-01131015019015019-510.1063/9.0000532Magnetic coupling of divalent metal centers in postsynthetic metal exchanged bimetallic DUT-49 MOFs by EPR spectroscopyKavipriya Thangavel0Matthias Mendt1Bikash Garai2Andrea Folli3Volodymyr Bon4Damien M. Murphy5Stefan Kaskel6Andreas Pöppl7Felix Bloch Institute for Solid State Physics, University of Leipzig, Linnestrasse. 5, 04103 Leipzig, GermanyFelix Bloch Institute for Solid State Physics, University of Leipzig, Linnestrasse. 5, 04103 Leipzig, GermanyDepartment of Inorganic Chemistry, Technische Universität Dresden, Bergstraße 66, 01069 Dresden, GermanySchool of Chemistry, Cardiff University, Park Place, Cardiff CF10 3AT, United KingdomDepartment of Inorganic Chemistry, Technische Universität Dresden, Bergstraße 66, 01069 Dresden, GermanySchool of Chemistry, Cardiff University, Park Place, Cardiff CF10 3AT, United KingdomDepartment of Inorganic Chemistry, Technische Universität Dresden, Bergstraße 66, 01069 Dresden, GermanyFelix Bloch Institute for Solid State Physics, University of Leipzig, Linnestrasse. 5, 04103 Leipzig, GermanyEPR measurements at X- (9.5 GHz), Q- (34 GHz) and W-band (94 GHz) on paddlewheel (PW) type post-synthetic metal exchanged DUT-49(M,M): M- Zn, Mn, Cu MOFs are here reported (DUT–Dresden University of Technology). Temperature-dependent X-band measurements are recorded from T = 7 K to T = 170 K on monometallic DUT-49(Cu), DUT-49(Mn), and bimetallic DUT-49(Cu0.7Zn0.3), DUT-49(Cu0.5Mn0.5) MOFs. In the case of the CuII - CuII dimers in DUT-49(Cu), an isotropic exchange coupling of the metal ions (2J = −240(11) cm−1) determined from the EPR intensity of the S = 1 spin state of the CuII–CuII dimers using the Bleaney Blowers equation. The sign of the found isotropic exchange coupling constant confirms an antiferromagnetic coupling between the cupric ions. Also, the MnII ions in the paddle wheels of DUT-49(Mn) are antiferromagnetically coupled. However, at low temperatures, EPR measurements reveal the presence of CuII and MnII monomers in DUT-49(Cu) and DUT-49(Mn), respectively, either associated with extra framework sites or defective paddle wheels. Otherwise, EPR signals observed for bimetallic DUT-49(Cu0.7Zn0.3) and DUT-49(Cu0.5Mn0.5) MOFs reveal the formation of mixed ion CuII–ZnII and CuII–MnII paddle wheels with SCuZn =1/2 and SCuMn = 2 spin states, respectively.http://dx.doi.org/10.1063/9.0000532 |
| spellingShingle | Kavipriya Thangavel Matthias Mendt Bikash Garai Andrea Folli Volodymyr Bon Damien M. Murphy Stefan Kaskel Andreas Pöppl Magnetic coupling of divalent metal centers in postsynthetic metal exchanged bimetallic DUT-49 MOFs by EPR spectroscopy AIP Advances |
| title | Magnetic coupling of divalent metal centers in postsynthetic metal exchanged bimetallic DUT-49 MOFs by EPR spectroscopy |
| title_full | Magnetic coupling of divalent metal centers in postsynthetic metal exchanged bimetallic DUT-49 MOFs by EPR spectroscopy |
| title_fullStr | Magnetic coupling of divalent metal centers in postsynthetic metal exchanged bimetallic DUT-49 MOFs by EPR spectroscopy |
| title_full_unstemmed | Magnetic coupling of divalent metal centers in postsynthetic metal exchanged bimetallic DUT-49 MOFs by EPR spectroscopy |
| title_short | Magnetic coupling of divalent metal centers in postsynthetic metal exchanged bimetallic DUT-49 MOFs by EPR spectroscopy |
| title_sort | magnetic coupling of divalent metal centers in postsynthetic metal exchanged bimetallic dut 49 mofs by epr spectroscopy |
| url | http://dx.doi.org/10.1063/9.0000532 |
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