Mixed-metal single-molecule magnets: Syntheses, structure, and magnetic properties of [Mn8Fe4O12(O2CR) 16(H2O)4] (R = CH2Cl, CH 2Br, CHCl2)

Chen I. Yang; Shwu Fen Yang; Shao Po Hung; Gene Hsiang Lee; Ching Shuei Wur; Hui Lien Tsai

doi:10.1016/j.poly.2011.02.002

Mixed-metal single-molecule magnets: Syntheses, structure, and magnetic properties of [Mn₈Fe₄O₁₂(O₂CR) ₁₆(H₂O)₄] (R = CH₂Cl, CH ₂Br, CHCl₂)

Chen I. Yang, Shwu Fen Yang, Shao Po Hung, Gene Hsiang Lee, Ching Shuei Wur, Hui Lien Tsai

Department of Chemistry

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Abstract

Three mixed-metal single-molecule magnets containing [Mn₈Fe ₄O₁₂]¹⁶⁺ cores are synthesized and characterized. The reaction of FeCl₂·4H₂O with KMnO₄ and RCOOH (R = CH₂Cl, CH₂Br) in H ₂O gives [Mn₈Fe₄O₁₂(O ₂CR)₁₆(H₂O)₄] (R = CH₂Cl (1), CH₂Br (2)) in yields of 43% and 40%, respectively. Treatment of complex 1 with an excess of CHCl₂COOH in CH₂Cl₂ gives [Mn₈Fe₄O₁₂(O₂CCHCl ₂)₁₆(H₂O)₄]·CH ₂Cl₂·10H₂O (3·CH ₂Cl₂·10H₂O) in a yield of 83%. The X-ray structure analysis reveals that all three complexes consist of a trapped-valence dodecanuclear core comprising 4Mn^III, 4Fe ^III, and 4Mn^IV ions. DC magnetic susceptibility and magnetization measurements indicate that all three complexes exhibit intramolecular antiferromagnetic interaction, resulting in an S = 4 ground state. In addition, frequency-dependent out-of-phase AC magnetic susceptibility signals at low temperature for complexes 1, 2, and 3 are indicative of their single-molecule magnetism behavior.

Original language	English
Pages (from-to)	2969-2977
Number of pages	9
Journal	Polyhedron
Volume	30
Issue number	18
DOIs	https://doi.org/10.1016/j.poly.2011.02.002
Publication status	Published - 2011 Nov 28

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.poly.2011.02.002

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@article{0ba70112422844de9b1e5355dca436b2,

title = "Mixed-metal single-molecule magnets: Syntheses, structure, and magnetic properties of [Mn8Fe4O12(O2CR) 16(H2O)4] (R = CH2Cl, CH 2Br, CHCl2)",

abstract = "Three mixed-metal single-molecule magnets containing [Mn8Fe 4O12]16+ cores are synthesized and characterized. The reaction of FeCl2·4H2O with KMnO4 and RCOOH (R = CH2Cl, CH2Br) in H 2O gives [Mn8Fe4O12(O 2CR)16(H2O)4] (R = CH2Cl (1), CH2Br (2)) in yields of 43% and 40%, respectively. Treatment of complex 1 with an excess of CHCl2COOH in CH2Cl2 gives [Mn8Fe4O12(O2CCHCl 2)16(H2O)4]·CH 2Cl2·10H2O (3·CH 2Cl2·10H2O) in a yield of 83%. The X-ray structure analysis reveals that all three complexes consist of a trapped-valence dodecanuclear core comprising 4MnIII, 4Fe III, and 4MnIV ions. DC magnetic susceptibility and magnetization measurements indicate that all three complexes exhibit intramolecular antiferromagnetic interaction, resulting in an S = 4 ground state. In addition, frequency-dependent out-of-phase AC magnetic susceptibility signals at low temperature for complexes 1, 2, and 3 are indicative of their single-molecule magnetism behavior.",

author = "Yang, {Chen I.} and Yang, {Shwu Fen} and Hung, {Shao Po} and Lee, {Gene Hsiang} and Wur, {Ching Shuei} and Tsai, {Hui Lien}",

note = "Funding Information: We would like to thank the National Science Council of the Republic of China for financial support under Grant NSC-99-2113-M-006-003-MY3 . ",

year = "2011",

month = nov,

day = "28",

doi = "10.1016/j.poly.2011.02.002",

language = "English",

volume = "30",

pages = "2969--2977",

journal = "Polyhedron",

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publisher = "Elsevier Limited",

number = "18",

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TY - JOUR

T1 - Mixed-metal single-molecule magnets

T2 - Syntheses, structure, and magnetic properties of [Mn8Fe4O12(O2CR) 16(H2O)4] (R = CH2Cl, CH 2Br, CHCl2)

AU - Yang, Chen I.

AU - Yang, Shwu Fen

AU - Hung, Shao Po

AU - Lee, Gene Hsiang

AU - Wur, Ching Shuei

AU - Tsai, Hui Lien

N1 - Funding Information: We would like to thank the National Science Council of the Republic of China for financial support under Grant NSC-99-2113-M-006-003-MY3 .

PY - 2011/11/28

Y1 - 2011/11/28

N2 - Three mixed-metal single-molecule magnets containing [Mn8Fe 4O12]16+ cores are synthesized and characterized. The reaction of FeCl2·4H2O with KMnO4 and RCOOH (R = CH2Cl, CH2Br) in H 2O gives [Mn8Fe4O12(O 2CR)16(H2O)4] (R = CH2Cl (1), CH2Br (2)) in yields of 43% and 40%, respectively. Treatment of complex 1 with an excess of CHCl2COOH in CH2Cl2 gives [Mn8Fe4O12(O2CCHCl 2)16(H2O)4]·CH 2Cl2·10H2O (3·CH 2Cl2·10H2O) in a yield of 83%. The X-ray structure analysis reveals that all three complexes consist of a trapped-valence dodecanuclear core comprising 4MnIII, 4Fe III, and 4MnIV ions. DC magnetic susceptibility and magnetization measurements indicate that all three complexes exhibit intramolecular antiferromagnetic interaction, resulting in an S = 4 ground state. In addition, frequency-dependent out-of-phase AC magnetic susceptibility signals at low temperature for complexes 1, 2, and 3 are indicative of their single-molecule magnetism behavior.

AB - Three mixed-metal single-molecule magnets containing [Mn8Fe 4O12]16+ cores are synthesized and characterized. The reaction of FeCl2·4H2O with KMnO4 and RCOOH (R = CH2Cl, CH2Br) in H 2O gives [Mn8Fe4O12(O 2CR)16(H2O)4] (R = CH2Cl (1), CH2Br (2)) in yields of 43% and 40%, respectively. Treatment of complex 1 with an excess of CHCl2COOH in CH2Cl2 gives [Mn8Fe4O12(O2CCHCl 2)16(H2O)4]·CH 2Cl2·10H2O (3·CH 2Cl2·10H2O) in a yield of 83%. The X-ray structure analysis reveals that all three complexes consist of a trapped-valence dodecanuclear core comprising 4MnIII, 4Fe III, and 4MnIV ions. DC magnetic susceptibility and magnetization measurements indicate that all three complexes exhibit intramolecular antiferromagnetic interaction, resulting in an S = 4 ground state. In addition, frequency-dependent out-of-phase AC magnetic susceptibility signals at low temperature for complexes 1, 2, and 3 are indicative of their single-molecule magnetism behavior.

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JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

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ER -

Mixed-metal single-molecule magnets: Syntheses, structure, and magnetic properties of [Mn₈Fe₄O₁₂(O₂CR) ₁₆(H₂O)₄] (R = CH₂Cl, CH ₂Br, CHCl₂)

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