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

doi:10.1021/ic3014333

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

40 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, [Mn^IIMn^III₃O]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 U_eff = 37 K for 2·1.5Et₂O.

Original language	English
Pages (from-to)	13171-13180
Number of pages	10
Journal	Inorganic Chemistry
Volume	51
Issue number	24
DOIs	https://doi.org/10.1021/ic3014333
Publication status	Published - 2012 Dec 17

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic3014333

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@article{20badfe3fc0f4f56a48511d5c02f4cda,

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, [MnIIMnIII3O]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 = "Tsai, {Hui Lien} and Yang, {Chen I.} and Wolfgang Wernsdorfer and Huang, {Siang Hua} and Jhan, {Siang Yu} and Liu, {Ming Hsuan} and Lee, {Gene Hsiang}",

year = "2012",

month = dec,

day = "17",

doi = "10.1021/ic3014333",

language = "English",

volume = "51",

pages = "13171--13180",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "24",

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TY - JOUR

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, [MnIIMnIII3O]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, [MnIIMnIII3O]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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JO - Inorganic Chemistry

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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

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