Mn4 single-molecule-magnet-based polymers of a one-dimensional helical chain and a three-dimensional network

Syntheses, crystal structures, and magnetic properties

Hui-Lien Tsai, Chen I. Yang, Wolfgang Wernsdorfer, Siang Hua Huang, Siang Yu Jhan, Ming Hsuan Liu, Gene Hsiang Lee

Research output: Contribution to journalArticle

37 Citations (Scopus)

Abstract

Two Mn4 single-molecule-magnet (SMM)-based coordination polymers, {[Mn4O(salox)3(N3) 3(DMF)2(H2O)(dpp)]·0.5MeOH}n (1·0.5MeOH; H2salox = salicylaldoxime; dpp = 1,3-di-4-pyridylpropane; DMF = N,N-dimethylformamide) and {[Mn 4O(Me-salox)3(N3)3(dpp) 1.5]·1.5Et2O}n (2·1.5Et 2O; Me-H2salox = hydroxyphenylethanone oxime), are self-assembled from Mn(ClO4)2·6H 2O/H2salox and Mn(ClO4)2· 6H2O/Me-H2salox systems with dpp and NaN3 in DMF/MeOH, respectively. Both compounds comprise a mixed-valence tetranuclear manganese core, [MnIIMnIII 3O]9+, which serves as a building unit for subsequent assembly via oximate and azido ligands. The flexible dpp ligand links with a Mn4 unit, leading to the formation of a one-dimensional helical structure in 1·0.5MeOH and a three-dimensional pcu network in 2·1.5Et2O. The magnetic data analysis shows that antiferromagnetic interactions within the Mn4 units resulted in S = 3/2 and 7/2 ground states for 1·0.5MeOH and 2·1.5Et2O, respectively. Both compounds show SMM behavior, as evidenced by frequency-dependent out-of-phase signals in alternating-current magnetic susceptibility and magnetic hysteresis loop studies with an energy barrier of Ueff = 37 K for 2·1.5Et2O.

Original languageEnglish
Pages (from-to)13171-13180
Number of pages10
JournalInorganic Chemistry
Volume51
Issue number24
DOIs
Publication statusPublished - 2012 Dec 17

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network synthesis
Magnets
Magnetic properties
Polymers
magnets
Crystal structure
magnetic properties
Ligands
Magnetic hysteresis
Dimethylformamide
Sodium Azide
ligands
crystal structure
Molecules
Oximes
Energy barriers
polymers
Manganese
Hysteresis loops
coordination polymers

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Tsai, Hui-Lien ; Yang, Chen I. ; Wernsdorfer, Wolfgang ; Huang, Siang Hua ; Jhan, Siang Yu ; Liu, Ming Hsuan ; Lee, Gene Hsiang. / Mn4 single-molecule-magnet-based polymers of a one-dimensional helical chain and a three-dimensional network : Syntheses, crystal structures, and magnetic properties. In: Inorganic Chemistry. 2012 ; Vol. 51, No. 24. pp. 13171-13180.
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title = "Mn4 single-molecule-magnet-based polymers of a one-dimensional helical chain and a three-dimensional network: Syntheses, crystal structures, and magnetic properties",
abstract = "Two Mn4 single-molecule-magnet (SMM)-based coordination polymers, {[Mn4O(salox)3(N3) 3(DMF)2(H2O)(dpp)]·0.5MeOH}n (1·0.5MeOH; H2salox = salicylaldoxime; dpp = 1,3-di-4-pyridylpropane; DMF = N,N-dimethylformamide) and {[Mn 4O(Me-salox)3(N3)3(dpp) 1.5]·1.5Et2O}n (2·1.5Et 2O; Me-H2salox = hydroxyphenylethanone oxime), are self-assembled from Mn(ClO4)2·6H 2O/H2salox and Mn(ClO4)2· 6H2O/Me-H2salox systems with dpp and NaN3 in DMF/MeOH, respectively. Both compounds comprise a mixed-valence tetranuclear manganese core, [MnIIMnIII 3O]9+, which serves as a building unit for subsequent assembly via oximate and azido ligands. The flexible dpp ligand links with a Mn4 unit, leading to the formation of a one-dimensional helical structure in 1·0.5MeOH and a three-dimensional pcu network in 2·1.5Et2O. The magnetic data analysis shows that antiferromagnetic interactions within the Mn4 units resulted in S = 3/2 and 7/2 ground states for 1·0.5MeOH and 2·1.5Et2O, respectively. Both compounds show SMM behavior, as evidenced by frequency-dependent out-of-phase signals in alternating-current magnetic susceptibility and magnetic hysteresis loop studies with an energy barrier of Ueff = 37 K for 2·1.5Et2O.",
author = "Hui-Lien Tsai and Yang, {Chen I.} and Wolfgang Wernsdorfer and Huang, {Siang Hua} and Jhan, {Siang Yu} and Liu, {Ming Hsuan} and Lee, {Gene Hsiang}",
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Mn4 single-molecule-magnet-based polymers of a one-dimensional helical chain and a three-dimensional network : Syntheses, crystal structures, and magnetic properties. / Tsai, Hui-Lien; Yang, Chen I.; Wernsdorfer, Wolfgang; Huang, Siang Hua; Jhan, Siang Yu; Liu, Ming Hsuan; Lee, Gene Hsiang.

In: Inorganic Chemistry, Vol. 51, No. 24, 17.12.2012, p. 13171-13180.

Research output: Contribution to journalArticle

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T1 - Mn4 single-molecule-magnet-based polymers of a one-dimensional helical chain and a three-dimensional network

T2 - Syntheses, crystal structures, and magnetic properties

AU - Tsai, Hui-Lien

AU - Yang, Chen I.

AU - Wernsdorfer, Wolfgang

AU - Huang, Siang Hua

AU - Jhan, Siang Yu

AU - Liu, Ming Hsuan

AU - Lee, Gene Hsiang

PY - 2012/12/17

Y1 - 2012/12/17

N2 - Two Mn4 single-molecule-magnet (SMM)-based coordination polymers, {[Mn4O(salox)3(N3) 3(DMF)2(H2O)(dpp)]·0.5MeOH}n (1·0.5MeOH; H2salox = salicylaldoxime; dpp = 1,3-di-4-pyridylpropane; DMF = N,N-dimethylformamide) and {[Mn 4O(Me-salox)3(N3)3(dpp) 1.5]·1.5Et2O}n (2·1.5Et 2O; Me-H2salox = hydroxyphenylethanone oxime), are self-assembled from Mn(ClO4)2·6H 2O/H2salox and Mn(ClO4)2· 6H2O/Me-H2salox systems with dpp and NaN3 in DMF/MeOH, respectively. Both compounds comprise a mixed-valence tetranuclear manganese core, [MnIIMnIII 3O]9+, which serves as a building unit for subsequent assembly via oximate and azido ligands. The flexible dpp ligand links with a Mn4 unit, leading to the formation of a one-dimensional helical structure in 1·0.5MeOH and a three-dimensional pcu network in 2·1.5Et2O. The magnetic data analysis shows that antiferromagnetic interactions within the Mn4 units resulted in S = 3/2 and 7/2 ground states for 1·0.5MeOH and 2·1.5Et2O, respectively. Both compounds show SMM behavior, as evidenced by frequency-dependent out-of-phase signals in alternating-current magnetic susceptibility and magnetic hysteresis loop studies with an energy barrier of Ueff = 37 K for 2·1.5Et2O.

AB - Two Mn4 single-molecule-magnet (SMM)-based coordination polymers, {[Mn4O(salox)3(N3) 3(DMF)2(H2O)(dpp)]·0.5MeOH}n (1·0.5MeOH; H2salox = salicylaldoxime; dpp = 1,3-di-4-pyridylpropane; DMF = N,N-dimethylformamide) and {[Mn 4O(Me-salox)3(N3)3(dpp) 1.5]·1.5Et2O}n (2·1.5Et 2O; Me-H2salox = hydroxyphenylethanone oxime), are self-assembled from Mn(ClO4)2·6H 2O/H2salox and Mn(ClO4)2· 6H2O/Me-H2salox systems with dpp and NaN3 in DMF/MeOH, respectively. Both compounds comprise a mixed-valence tetranuclear manganese core, [MnIIMnIII 3O]9+, which serves as a building unit for subsequent assembly via oximate and azido ligands. The flexible dpp ligand links with a Mn4 unit, leading to the formation of a one-dimensional helical structure in 1·0.5MeOH and a three-dimensional pcu network in 2·1.5Et2O. The magnetic data analysis shows that antiferromagnetic interactions within the Mn4 units resulted in S = 3/2 and 7/2 ground states for 1·0.5MeOH and 2·1.5Et2O, respectively. Both compounds show SMM behavior, as evidenced by frequency-dependent out-of-phase signals in alternating-current magnetic susceptibility and magnetic hysteresis loop studies with an energy barrier of Ueff = 37 K for 2·1.5Et2O.

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