What Controls the Sign and Magnitude of Magnetic Anisotropy in Tetrahedral Cobalt(II) Single-Ion Magnets?
Identifieur interne : 001437 ( Main/Exploration ); précédent : 001436; suivant : 001438What Controls the Sign and Magnitude of Magnetic Anisotropy in Tetrahedral Cobalt(II) Single-Ion Magnets?
Auteurs : Shefali Vaidya ; Subrata Tewary ; Saurabh Kumar Singh ; Stuart K. Langley [Royaume-Uni] ; Keith S. Murray [Australie] ; Yanhua Lan [France] ; Wolfgang Wernsdorfer [France] ; Gopalan Rajaraman ; Maheswaran ShanmugamSource :
- Inorganic chemistry [ 1520-510X ] ; 2016.
Abstract
A family of mononuclear tetrahedral cobalt(II) thiourea complexes, [Co(L1)4](NO3)2 (1) and [Co(Lx)4](ClO4)2 where x = 2 (2), 3 (3), 4 (4) (where L1 = thiourea, L2 = 1,3-dibutylthiourea, L3 = 1,3-phenylethylthiourea, and L4 = 1,1,3,3-tetramethylthiourea), has been synthesized using a rationally designed synthetic approach, with the aim of stabilizing an Ising-type magnetic anisotropy (-D). On the basis of direct-current, alternating-current, and hysteresis magnetic measurements and theoretical calculations, we have identified the factors that govern the sign and magnitude of D and ultimately the ability to design a single-ion magnet for a tetrahedral cobalt(II) ion. To better understand the magnetization relaxation dynamics, particularly for complexes 1 and 2, dilution experiments were performed using their diamagnetic analogues, which are characterized by single-crystal X-ray diffraction with the general molecular formulas of [Zn(L1)4](NO3)2 (5) and [Zn(L2)4](ClO4)2 (6). Interestingly, intermolecular interactions are shown to play a role in quenching the quantum tunneling of magnetization in zero field, as evidenced in the hysteresis loop of 1. Complex 2 exhibits the largest Ueff value of 62 cm(-1) and reveals open hysteresis loops below 4 K. Furthermore, the influence of the hyperfine interaction on the magnetization relaxation dynamics is witnessed in the hysteresis loops, allowing us to determine the electron/nuclear spin S(Co) = (3)/2/I(Co) = (7)/2 hyperfine coupling constant of 550 MHz, a method ideally suited to determine the hyperfine coupling constant of highly anisotropic metal ions stabilized with large D value, which are otherwise hard to determine by conventional methods such as electron paramagnetic resonance.
DOI: 10.1021/acs.inorgchem.6b01073
PubMed: 27652694
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Langley</name><affiliation wicri:level="1"><nlm:affiliation>School of Science and the Environment, Chemistry Division, Manchester Metropolitan University , Manchester M15 6HB, U.K.</nlm:affiliation><country xml:lang="fr">Royaume-Uni</country><wicri:regionArea>School of Science and the Environment, Chemistry Division, Manchester Metropolitan University , Manchester M15 6HB</wicri:regionArea><wicri:noRegion>Manchester M15 6HB</wicri:noRegion></affiliation></author><author><name sortKey="Murray, Keith S" sort="Murray, Keith S" uniqKey="Murray K" first="Keith S" last="Murray">Keith S. Murray</name><affiliation wicri:level="1"><nlm:affiliation>School of Chemistry, Monash University , Clayton 3800, Victoria, Australia.</nlm:affiliation><country xml:lang="fr">Australie</country><wicri:regionArea>School of Chemistry, Monash University , Clayton 3800, Victoria</wicri:regionArea><wicri:noRegion>Victoria</wicri:noRegion></affiliation></author><author><name sortKey="Lan, Yanhua" sort="Lan, Yanhua" uniqKey="Lan Y" first="Yanhua" last="Lan">Yanhua Lan</name><affiliation wicri:level="1"><nlm:affiliation>Institut Néel, CNRS and Université Grenoble Alpes , BP 166, 25 Avenue des Martyrs, 38042 Grenoble Cedex 9, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Institut Néel, CNRS and Université Grenoble Alpes , BP 166, 25 Avenue des Martyrs, 38042 Grenoble Cedex 9</wicri:regionArea><wicri:noRegion>38042 Grenoble Cedex 9</wicri:noRegion><wicri:noRegion>38042 Grenoble Cedex 9</wicri:noRegion></affiliation></author><author><name sortKey="Wernsdorfer, Wolfgang" sort="Wernsdorfer, Wolfgang" uniqKey="Wernsdorfer W" first="Wolfgang" last="Wernsdorfer">Wolfgang Wernsdorfer</name><affiliation wicri:level="1"><nlm:affiliation>Institut Néel, CNRS and Université Grenoble Alpes , BP 166, 25 Avenue des Martyrs, 38042 Grenoble Cedex 9, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Institut Néel, CNRS and Université Grenoble Alpes , BP 166, 25 Avenue des Martyrs, 38042 Grenoble Cedex 9</wicri:regionArea><wicri:noRegion>38042 Grenoble Cedex 9</wicri:noRegion><wicri:noRegion>38042 Grenoble Cedex 9</wicri:noRegion></affiliation></author><author><name sortKey="Rajaraman, Gopalan" sort="Rajaraman, Gopalan" uniqKey="Rajaraman G" first="Gopalan" last="Rajaraman">Gopalan Rajaraman</name><affiliation><nlm:affiliation>Department of Chemistry, Indian Institute of Technology Bombay , Powai, Mumbai 400076, Maharashtra India.</nlm:affiliation><wicri:noCountry code="subField">Maharashtra India</wicri:noCountry></affiliation></author><author><name sortKey="Shanmugam, Maheswaran" sort="Shanmugam, Maheswaran" uniqKey="Shanmugam M" first="Maheswaran" last="Shanmugam">Maheswaran Shanmugam</name><affiliation><nlm:affiliation>Department of Chemistry, Indian Institute of Technology Bombay , Powai, Mumbai 400076, Maharashtra India.</nlm:affiliation><wicri:noCountry code="subField">Maharashtra India</wicri:noCountry></affiliation></author></analytic><series><title level="j">Inorganic chemistry</title><idno type="eISSN">1520-510X</idno><imprint><date when="2016" type="published">2016</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">A family of mononuclear tetrahedral cobalt(II) thiourea complexes, [Co(L1)4](NO3)2 (1) and [Co(Lx)4](ClO4)2 where x = 2 (2), 3 (3), 4 (4) (where L1 = thiourea, L2 = 1,3-dibutylthiourea, L3 = 1,3-phenylethylthiourea, and L4 = 1,1,3,3-tetramethylthiourea), has been synthesized using a rationally designed synthetic approach, with the aim of stabilizing an Ising-type magnetic anisotropy (-D). On the basis of direct-current, alternating-current, and hysteresis magnetic measurements and theoretical calculations, we have identified the factors that govern the sign and magnitude of D and ultimately the ability to design a single-ion magnet for a tetrahedral cobalt(II) ion. To better understand the magnetization relaxation dynamics, particularly for complexes 1 and 2, dilution experiments were performed using their diamagnetic analogues, which are characterized by single-crystal X-ray diffraction with the general molecular formulas of [Zn(L1)4](NO3)2 (5) and [Zn(L2)4](ClO4)2 (6). Interestingly, intermolecular interactions are shown to play a role in quenching the quantum tunneling of magnetization in zero field, as evidenced in the hysteresis loop of 1. Complex 2 exhibits the largest Ueff value of 62 cm(-1) and reveals open hysteresis loops below 4 K. Furthermore, the influence of the hyperfine interaction on the magnetization relaxation dynamics is witnessed in the hysteresis loops, allowing us to determine the electron/nuclear spin S(Co) = (3)/2/I(Co) = (7)/2 hyperfine coupling constant of 550 MHz, a method ideally suited to determine the hyperfine coupling constant of highly anisotropic metal ions stabilized with large D value, which are otherwise hard to determine by conventional methods such as electron paramagnetic resonance.</div></front></TEI><affiliations><list><country><li>Australie</li><li>France</li><li>Royaume-Uni</li></country></list><tree><noCountry><name sortKey="Rajaraman, Gopalan" sort="Rajaraman, Gopalan" uniqKey="Rajaraman G" first="Gopalan" last="Rajaraman">Gopalan Rajaraman</name><name sortKey="Shanmugam, Maheswaran" sort="Shanmugam, Maheswaran" uniqKey="Shanmugam M" first="Maheswaran" last="Shanmugam">Maheswaran Shanmugam</name><name sortKey="Singh, Saurabh Kumar" sort="Singh, Saurabh Kumar" uniqKey="Singh S" first="Saurabh Kumar" last="Singh">Saurabh Kumar Singh</name><name sortKey="Tewary, Subrata" sort="Tewary, Subrata" uniqKey="Tewary S" first="Subrata" last="Tewary">Subrata Tewary</name><name sortKey="Vaidya, Shefali" sort="Vaidya, Shefali" uniqKey="Vaidya S" first="Shefali" last="Vaidya">Shefali Vaidya</name></noCountry><country name="Royaume-Uni"><noRegion><name sortKey="Langley, Stuart K" sort="Langley, Stuart K" uniqKey="Langley S" first="Stuart K" last="Langley">Stuart K. Langley</name></noRegion></country><country name="Australie"><noRegion><name sortKey="Murray, Keith S" sort="Murray, Keith S" uniqKey="Murray K" first="Keith S" last="Murray">Keith S. Murray</name></noRegion></country><country name="France"><noRegion><name sortKey="Lan, Yanhua" sort="Lan, Yanhua" uniqKey="Lan Y" first="Yanhua" last="Lan">Yanhua Lan</name></noRegion><name sortKey="Wernsdorfer, Wolfgang" sort="Wernsdorfer, Wolfgang" uniqKey="Wernsdorfer W" first="Wolfgang" last="Wernsdorfer">Wolfgang Wernsdorfer</name></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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