From pseudo to true C3 symmetry: Magnetic anisotropy enhanced by site-specific ligand substitution in two Mn15-carboxylate clusters

Yan Zhen Zheng; Wei Xue; Wei Xiong Zhang; Ming Liang Tong; Xiao Ming Chen

doi:10.1021/ic7004584

From pseudo to true C₃ symmetry: Magnetic anisotropy enhanced by site-specific ligand substitution in two Mn₁₅-carboxylate clusters

Yan Zhen Zheng
, Wei Xue
, Wei Xiong Zhang
, Ming Liang Tong
, Xiao Ming Chen

Sun Yat-Sen University

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

50 Scopus citations

Abstract

Two new mixed-valence manganese-carboxylate clusters, [Mn ^III₉Mn^IV₆(O₂CPh) ₁₂(μ₃-O)₁₃(μ-O)₄(μ-OMe) ₅(MeOH)₄(H₂O)₅]₂· 1.5PhCO₂H·MeOH·6H₂O (1, PhCO₂H = benzoic acid) and [Mn^III₉Mn^IV ₆(O₂CCh)₁₂(μ₃-O) ₁₃(μ-O)₄(μ-OMe)₅(MeOH)₃(H ₂O)₆]·0.5MeOH·2.5H₂O (2, ChCO₂H= cyclohexanecarboxylic acid) contain new disklike Mn ₁₅ cores. Both 1 and 2 can be synthesized by the conventional manganese redox reaction (MnO₄^- oxidizing Mn²⁺) in methanol solution. 2 can be also synthesized via the site-specific ligand substitution reaction from 1. 1 crystallizes in the triclinic space group P1, whereas 2 crystallizes in the trigonal space group P3. Magnetic study shows that both 1 and 2 have the same ground spin states S_T = 2. Compared to the silence of the out-of-phase ac susceptibility of 1, 2 shows clearly slow magnetic relaxation behavior above 1.8 K due to the dramatically enhanced axial magnetic anisotropy (D = -0.89 and -1.58 cm^-1 for 1 and 2, respectively, which was obtained by fitting the plots of M vs H/T with the program ANISOFIT 2.0).

Original language	English
Pages (from-to)	6437-6443
Number of pages	7
Journal	Inorganic Chemistry
Volume	46
Issue number	16
DOIs	https://doi.org/10.1021/ic7004584
State	Published - 6 Aug 2007
Externally published	Yes

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@article{19bf9a02fc5e45b097847abfa92dc72c,

title = "From pseudo to true C3 symmetry: Magnetic anisotropy enhanced by site-specific ligand substitution in two Mn15-carboxylate clusters",

abstract = "Two new mixed-valence manganese-carboxylate clusters, [Mn III9MnIV6(O2CPh) 12(μ3-O)13(μ-O)4(μ-OMe) 5(MeOH)4(H2O)5]2· 1.5PhCO2H·MeOH·6H2O (1, PhCO2H = benzoic acid) and [MnIII9MnIV 6(O2CCh)12(μ3-O) 13(μ-O)4(μ-OMe)5(MeOH)3(H 2O)6]·0.5MeOH·2.5H2O (2, ChCO2H= cyclohexanecarboxylic acid) contain new disklike Mn 15 cores. Both 1 and 2 can be synthesized by the conventional manganese redox reaction (MnO4- oxidizing Mn2+) in methanol solution. 2 can be also synthesized via the site-specific ligand substitution reaction from 1. 1 crystallizes in the triclinic space group P1, whereas 2 crystallizes in the trigonal space group P3. Magnetic study shows that both 1 and 2 have the same ground spin states ST = 2. Compared to the silence of the out-of-phase ac susceptibility of 1, 2 shows clearly slow magnetic relaxation behavior above 1.8 K due to the dramatically enhanced axial magnetic anisotropy (D = -0.89 and -1.58 cm-1 for 1 and 2, respectively, which was obtained by fitting the plots of M vs H/T with the program ANISOFIT 2.0).",

author = "Zheng, \{Yan Zhen\} and Wei Xue and Zhang, \{Wei Xiong\} and Tong, \{Ming Liang\} and Chen, \{Xiao Ming\}",

year = "2007",

month = aug,

day = "6",

doi = "10.1021/ic7004584",

language = "英语",

volume = "46",

pages = "6437--6443",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "16",

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TY - JOUR

T1 - From pseudo to true C3 symmetry

T2 - Magnetic anisotropy enhanced by site-specific ligand substitution in two Mn15-carboxylate clusters

AU - Zheng, Yan Zhen

AU - Xue, Wei

AU - Zhang, Wei Xiong

AU - Tong, Ming Liang

AU - Chen, Xiao Ming

PY - 2007/8/6

Y1 - 2007/8/6

N2 - Two new mixed-valence manganese-carboxylate clusters, [Mn III9MnIV6(O2CPh) 12(μ3-O)13(μ-O)4(μ-OMe) 5(MeOH)4(H2O)5]2· 1.5PhCO2H·MeOH·6H2O (1, PhCO2H = benzoic acid) and [MnIII9MnIV 6(O2CCh)12(μ3-O) 13(μ-O)4(μ-OMe)5(MeOH)3(H 2O)6]·0.5MeOH·2.5H2O (2, ChCO2H= cyclohexanecarboxylic acid) contain new disklike Mn 15 cores. Both 1 and 2 can be synthesized by the conventional manganese redox reaction (MnO4- oxidizing Mn2+) in methanol solution. 2 can be also synthesized via the site-specific ligand substitution reaction from 1. 1 crystallizes in the triclinic space group P1, whereas 2 crystallizes in the trigonal space group P3. Magnetic study shows that both 1 and 2 have the same ground spin states ST = 2. Compared to the silence of the out-of-phase ac susceptibility of 1, 2 shows clearly slow magnetic relaxation behavior above 1.8 K due to the dramatically enhanced axial magnetic anisotropy (D = -0.89 and -1.58 cm-1 for 1 and 2, respectively, which was obtained by fitting the plots of M vs H/T with the program ANISOFIT 2.0).

AB - Two new mixed-valence manganese-carboxylate clusters, [Mn III9MnIV6(O2CPh) 12(μ3-O)13(μ-O)4(μ-OMe) 5(MeOH)4(H2O)5]2· 1.5PhCO2H·MeOH·6H2O (1, PhCO2H = benzoic acid) and [MnIII9MnIV 6(O2CCh)12(μ3-O) 13(μ-O)4(μ-OMe)5(MeOH)3(H 2O)6]·0.5MeOH·2.5H2O (2, ChCO2H= cyclohexanecarboxylic acid) contain new disklike Mn 15 cores. Both 1 and 2 can be synthesized by the conventional manganese redox reaction (MnO4- oxidizing Mn2+) in methanol solution. 2 can be also synthesized via the site-specific ligand substitution reaction from 1. 1 crystallizes in the triclinic space group P1, whereas 2 crystallizes in the trigonal space group P3. Magnetic study shows that both 1 and 2 have the same ground spin states ST = 2. Compared to the silence of the out-of-phase ac susceptibility of 1, 2 shows clearly slow magnetic relaxation behavior above 1.8 K due to the dramatically enhanced axial magnetic anisotropy (D = -0.89 and -1.58 cm-1 for 1 and 2, respectively, which was obtained by fitting the plots of M vs H/T with the program ANISOFIT 2.0).

UR - https://www.scopus.com/pages/publications/34548043495

U2 - 10.1021/ic7004584

DO - 10.1021/ic7004584

M3 - 文章

C2 - 17630682

AN - SCOPUS:34548043495

SN - 0020-1669

VL - 46

SP - 6437

EP - 6443

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 16

ER -

From pseudo to true C₃ symmetry: Magnetic anisotropy enhanced by site-specific ligand substitution in two Mn₁₅-carboxylate clusters

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