A SIM-MOF: Three-Dimensional Organisation of Single-Ion Magnets with Anion-Exchange Capabilities

The formation of a metal–organic framework (MOF) with nodes that have single‐molecule magnet (SMM) behaviour has been achieved by using mononuclear lanthanoid analogues, also known as single‐ion magnets (SIMs), which enormously simplifies the challenging issue of making SMM‐MOFs. Here we present a r...

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Vydáno v:Chemistry : a European journal Ročník 20; číslo 34; s. 10695 - 10702
Hlavní autoři: Baldoví, José J., Coronado, Eugenio, Gaita-Ariño, Alejandro, Gamer, Christoph, Giménez-Marqués, Mónica, Mínguez Espallargas, Guillermo
Médium: Journal Article
Jazyk:angličtina
Vydáno: Weinheim WILEY-VCH Verlag 18.08.2014
WILEY‐VCH Verlag
Wiley Subscription Services, Inc
Témata:
Acetal resins
Anion exchange
Anions
Chemistry
Holes
Magnetic fields
magnetic properties
Magnetic relaxation
Magnets
metal-organic frameworks
Metalorganic compounds
polyoxometalates
Polyoxometallates
Robustness
single-molecule studies
Three dimensional
magnetic properties
anions
polyoxometalates
metal-organic frameworks
single-molecule studies
ISSN:0947-6539, 1521-3765, 1521-3765
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Abstract The formation of a metal–organic framework (MOF) with nodes that have single‐molecule magnet (SMM) behaviour has been achieved by using mononuclear lanthanoid analogues, also known as single‐ion magnets (SIMs), which enormously simplifies the challenging issue of making SMM‐MOFs. Here we present a rational design of a family of MOFs, [Ln(bipyNO)4](TfO)3⋅x solvent (Ln=Tb (1); Dy (2); Ho (3); Er (4); TfO=triflate), in which the lanthanoid centres have an square‐antiprismatic coordination environment suitable for SIM behaviour. Magnetic measurements confirm the existence of slow magnetic relaxation typical of SMMs, which has been rationalised by means of a radial effective charge model. In addition, we have explored the incorporation of bulky polyoxometalates (POMs) into the cavities of the SIM‐MOF by anion exchange, finding that they do not interfere with the slow magnetic relaxation. This demonstrates the robustness of the frameworks and opens the possibility of incorporating non‐innocent anions. SIMs to be in (3D) order: The formation of a single‐ion magnet/metal–organic framework (SIM‐MOF) is presented, which enormously simplifies the challenging issue of making SMM‐MOFs. The incorporation of bulky polyoxometalates (POMs) into the cavities does not interfere with the slow magnetic relaxation, demonstrating the robustness of the frameworks and opening the possibility of incorporating non‐innocent anions.
AbstractList The formation of a metal-organic framework (MOF) with nodes that have single-molecule magnet (SMM) behaviour has been achieved by using mononuclear lanthanoid analogues, also known as single-ion magnets (SIMs), which enormously simplifies the challenging issue of making SMM-MOFs. Here we present a rational design of a family of MOFs, [Ln(bipyNO)4](TfO)3⋅x solvent (Ln=Tb (1); Dy (2); Ho (3); Er (4); TfO=triflate), in which the lanthanoid centres have an square-antiprismatic coordination environment suitable for SIM behaviour. Magnetic measurements confirm the existence of slow magnetic relaxation typical of SMMs, which has been rationalised by means of a radial effective charge model. In addition, we have explored the incorporation of bulky polyoxometalates (POMs) into the cavities of the SIM-MOF by anion exchange, finding that they do not interfere with the slow magnetic relaxation. This demonstrates the robustness of the frameworks and opens the possibility of incorporating non-innocent anions.
The formation of a metal-organic framework (MOF) with nodes that have single-molecule magnet (SMM) behaviour has been achieved by using mononuclear lanthanoid analogues, also known as single-ion magnets (SIMs), which enormously simplifies the challenging issue of making SMM-MOFs. Here we present a rational design of a family of MOFs, [Ln(bipyNO) sub(4)](TfO) sub(3) x solvent (Ln=Tb (1); Dy (2); Ho (3); Er (4); TfO=triflate), in which the lanthanoid centres have an square-antiprismatic coordination environment suitable for SIM behaviour. Magnetic measurements confirm the existence of slow magnetic relaxation typical of SMMs, which has been rationalised by means of a radial effective charge model. In addition, we have explored the incorporation of bulky polyoxometalates (POMs) into the cavities of the SIM-MOF by anion exchange, finding that they do not interfere with the slow magnetic relaxation. This demonstrates the robustness of the frameworks and opens the possibility of incorporating non-innocent anions. SIMs to be in (3D) order: The formation of a single-ion magnet/metal-organic framework (SIM-MOF) is presented, which enormously simplifies the challenging issue of making SMM-MOFs. The incorporation of bulky polyoxometalates (POMs) into the cavities does not interfere with the slow magnetic relaxation, demonstrating the robustness of the frameworks and opening the possibility of incorporating non-innocent anions.
The formation of a metal–organic framework (MOF) with nodes that have single‐molecule magnet (SMM) behaviour has been achieved by using mononuclear lanthanoid analogues, also known as single‐ion magnets (SIMs), which enormously simplifies the challenging issue of making SMM‐MOFs. Here we present a rational design of a family of MOFs, [ Ln(bipyNO) 4 ](TfO) 3 ⋅ x solvent (Ln=Tb ( 1 ); Dy ( 2 ); Ho ( 3 ); Er ( 4 ); TfO=triflate), in which the lanthanoid centres have an square‐antiprismatic coordination environment suitable for SIM behaviour. Magnetic measurements confirm the existence of slow magnetic relaxation typical of SMMs, which has been rationalised by means of a radial effective charge model. In addition, we have explored the incorporation of bulky polyoxometalates (POMs) into the cavities of the SIM‐MOF by anion exchange, finding that they do not interfere with the slow magnetic relaxation. This demonstrates the robustness of the frameworks and opens the possibility of incorporating non‐innocent anions.
The formation of a metal–organic framework (MOF) with nodes that have single‐molecule magnet (SMM) behaviour has been achieved by using mononuclear lanthanoid analogues, also known as single‐ion magnets (SIMs), which enormously simplifies the challenging issue of making SMM‐MOFs. Here we present a rational design of a family of MOFs, [Ln(bipyNO)4](TfO)3⋅x solvent (Ln=Tb (1); Dy (2); Ho (3); Er (4); TfO=triflate), in which the lanthanoid centres have an square‐antiprismatic coordination environment suitable for SIM behaviour. Magnetic measurements confirm the existence of slow magnetic relaxation typical of SMMs, which has been rationalised by means of a radial effective charge model. In addition, we have explored the incorporation of bulky polyoxometalates (POMs) into the cavities of the SIM‐MOF by anion exchange, finding that they do not interfere with the slow magnetic relaxation. This demonstrates the robustness of the frameworks and opens the possibility of incorporating non‐innocent anions. SIMs to be in (3D) order: The formation of a single‐ion magnet/metal–organic framework (SIM‐MOF) is presented, which enormously simplifies the challenging issue of making SMM‐MOFs. The incorporation of bulky polyoxometalates (POMs) into the cavities does not interfere with the slow magnetic relaxation, demonstrating the robustness of the frameworks and opening the possibility of incorporating non‐innocent anions.
The formation of a metal-organic framework (MOF) with nodes that have single-molecule magnet (SMM) behaviour has been achieved by using mononuclear lanthanoid analogues, also known as single-ion magnets (SIMs), which enormously simplifies the challenging issue of making SMM-MOFs. Here we present a rational design of a family of MOFs, [Ln(bipyNO)4](TfO)3⋅x solvent (Ln=Tb (1); Dy (2); Ho (3); Er (4); TfO=triflate), in which the lanthanoid centres have an square-antiprismatic coordination environment suitable for SIM behaviour. Magnetic measurements confirm the existence of slow magnetic relaxation typical of SMMs, which has been rationalised by means of a radial effective charge model. In addition, we have explored the incorporation of bulky polyoxometalates (POMs) into the cavities of the SIM-MOF by anion exchange, finding that they do not interfere with the slow magnetic relaxation. This demonstrates the robustness of the frameworks and opens the possibility of incorporating non-innocent anions.The formation of a metal-organic framework (MOF) with nodes that have single-molecule magnet (SMM) behaviour has been achieved by using mononuclear lanthanoid analogues, also known as single-ion magnets (SIMs), which enormously simplifies the challenging issue of making SMM-MOFs. Here we present a rational design of a family of MOFs, [Ln(bipyNO)4](TfO)3⋅x solvent (Ln=Tb (1); Dy (2); Ho (3); Er (4); TfO=triflate), in which the lanthanoid centres have an square-antiprismatic coordination environment suitable for SIM behaviour. Magnetic measurements confirm the existence of slow magnetic relaxation typical of SMMs, which has been rationalised by means of a radial effective charge model. In addition, we have explored the incorporation of bulky polyoxometalates (POMs) into the cavities of the SIM-MOF by anion exchange, finding that they do not interfere with the slow magnetic relaxation. This demonstrates the robustness of the frameworks and opens the possibility of incorporating non-innocent anions.
The formation of a metal-organic framework (MOF) with nodes that have single-molecule magnet (SMM) behaviour has been achieved by using mononuclear lanthanoid analogues, also known as single-ion magnets (SIMs), which enormously simplifies the challenging issue of making SMM-MOFs. Here we present a rational design of a family of MOFs, [Ln(bipyNO)4](TfO)3xsolvent (Ln=Tb (1); Dy (2); Ho (3); Er (4); TfO=triflate), in which the lanthanoid centres have an square-antiprismatic coordination environment suitable for SIM behaviour. Magnetic measurements confirm the existence of slow magnetic relaxation typical of SMMs, which has been rationalised by means of a radial effective charge model. In addition, we have explored the incorporation of bulky polyoxometalates (POMs) into the cavities of the SIM-MOF by anion exchange, finding that they do not interfere with the slow magnetic relaxation. This demonstrates the robustness of the frameworks and opens the possibility of incorporating non-innocent anions. [PUBLICATION ABSTRACT]
Author Giménez-Marqués, Mónica
Gamer, Christoph
Coronado, Eugenio
Gaita-Ariño, Alejandro
Mínguez Espallargas, Guillermo
Baldoví, José J.
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  surname: Baldoví
  fullname: Baldoví, José J.
  organization: Instituto de Ciencia Molecular (ICMol), Universidad de Valencia c/Catedrático José Beltrán, 2, 46980 Paterna (Spain)
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  givenname: Eugenio
  surname: Coronado
  fullname: Coronado, Eugenio
  email: eugenio.coronado@uv.es
  organization: Instituto de Ciencia Molecular (ICMol), Universidad de Valencia c/Catedrático José Beltrán, 2, 46980 Paterna (Spain)
– sequence: 3
  givenname: Alejandro
  surname: Gaita-Ariño
  fullname: Gaita-Ariño, Alejandro
  organization: Instituto de Ciencia Molecular (ICMol), Universidad de Valencia c/Catedrático José Beltrán, 2, 46980 Paterna (Spain)
– sequence: 4
  givenname: Christoph
  surname: Gamer
  fullname: Gamer, Christoph
  organization: Instituto de Ciencia Molecular (ICMol), Universidad de Valencia c/Catedrático José Beltrán, 2, 46980 Paterna (Spain)
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  givenname: Mónica
  surname: Giménez-Marqués
  fullname: Giménez-Marqués, Mónica
  organization: Instituto de Ciencia Molecular (ICMol), Universidad de Valencia c/Catedrático José Beltrán, 2, 46980 Paterna (Spain)
– sequence: 6
  givenname: Guillermo
  surname: Mínguez Espallargas
  fullname: Mínguez Espallargas, Guillermo
  email: guillermo.minguez@uv.es
  organization: Instituto de Ciencia Molecular (ICMol), Universidad de Valencia c/Catedrático José Beltrán, 2, 46980 Paterna (Spain)
BackLink https://www.ncbi.nlm.nih.gov/pubmed/24804629$$D View this record in MEDLINE/PubMed
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2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Issue 34
Keywords magnetic properties
anions
polyoxometalates
metal-organic frameworks
single-molecule studies
Language English
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2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Spanish MINECO - No. MAT2011-22785; No. CTQ2011-26507
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SIM-MOF=single-ion magnet/metal-organic framework.
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PublicationDate August 18, 2014
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  text: August 18, 2014
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PublicationSubtitle A European Journal
PublicationTitle Chemistry : a European journal
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Snippet The formation of a metal–organic framework (MOF) with nodes that have single‐molecule magnet (SMM) behaviour has been achieved by using mononuclear lanthanoid...
The formation of a metal-organic framework (MOF) with nodes that have single-molecule magnet (SMM) behaviour has been achieved by using mononuclear lanthanoid...
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StartPage 10695
SubjectTerms Acetal resins
Anion exchange
Anions
Chemistry
Holes
Magnetic fields
magnetic properties
Magnetic relaxation
Magnets
metal-organic frameworks
Metalorganic compounds
polyoxometalates
Polyoxometallates
Robustness
single-molecule studies
Three dimensional
Title A SIM-MOF: Three-Dimensional Organisation of Single-Ion Magnets with Anion-Exchange Capabilities
URI https://api.istex.fr/ark:/67375/WNG-9DZMLC0J-X/fulltext.pdf
https://onlinelibrary.wiley.com/doi/abs/10.1002%2Fchem.201402255
https://www.ncbi.nlm.nih.gov/pubmed/24804629
https://www.proquest.com/docview/1552550019
https://www.proquest.com/docview/1554469091
https://www.proquest.com/docview/1778044228
Volume 20
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