Mixed-valence tetra- and hexanuclear manganese complexes from the flexibility of pyridine-containing β-diketone ligands

Chen I. Yang, Wolfgang Wernsdorfer, Yu Jhe Tsai, George Chung, Ting Shen Kuo, Gene Hsiang Lee, Minghuey Shieh, Hui-Lien Tsai

Research output: Contribution to journalArticle

37 Citations (Scopus)

Abstract

The reactions of [Mn3O(O2CCCl3) 6(H2O)3] with 1-phenyl-3-(2-pyridyl)propane-1, 3-dione (HL1) and 1-(2-pyridly)-3-(p-tolyl)propane-1,3-dione (HL 2) in CH2Cl2 afford the mixed-valence Mn II2MnIII2 tetranuclear complexes [Mn4O-(O2CCCl3)6(L1) 2] (1) and [Mn4O(O2CCCl3) 6L22] (2), respectively. Similar reactions employing [Mn3O(O2CPh)6(H2O)(py) 2] with HL1 and HL2 give the Mn II3MnIII3 hexanuclear complexes [Mn6O2(O2CPh)8(L1) 3] (3) and [Mn6O2(O2CPh) 8L32] (4), respectively. Complexes 1·2CH2Cl2, 2·2CH2Cl 2·H2O, 3·1.5CH2Cl 2·Et2O·H2O, and 4·2CH 2Cl2 crystallize in the triclinic space group P1, monoclinic space group P21/c, monoclinic space group P2 1/n, and monoclinic space group P21/n, respectively. Complexes 1 and 2 consist of a trapped-valence tetranuclear core of [Mn II2MnIII24-0)] 8+, and complexes 3 and 4 represent a new structural type, possessing a [MnII3MnIII34-O) 2]11+ core. The magnetic data indicate that complexes 3 and 4 have a ground-state spin value of S = 7/2 with significant magnetoanisotropy as gauged by the D values of -0.51 cm-1 and -0.46 cm-1, respectively, and frequency-dependent out-of-phase signals in alternating current magnetic susceptibility studies indicate their superparamagnetic behavior. In contrast, complexes 1 and 2 are low-spin molecules with an S = 1 ground state. Single-molecule magnetism behavior confirmed for 3 the presence of sweep-rate and temperature-dependent hysteresis loops in single-crystal M versus H studies at temperatures down to 40 mK.

Original languageEnglish
Pages (from-to)1925-1939
Number of pages15
JournalInorganic Chemistry
Volume47
Issue number6
DOIs
Publication statusPublished - 2008 Mar 17

Fingerprint

Propane
Manganese
Ground state
manganese
pyridines
flexibility
Ligands
valence
ligands
Molecules
Magnetism
Dione
Hysteresis loops
Magnetic susceptibility
propane
Single crystals
Temperature
ground state
molecules
alternating current

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Yang, Chen I. ; Wernsdorfer, Wolfgang ; Tsai, Yu Jhe ; Chung, George ; Kuo, Ting Shen ; Lee, Gene Hsiang ; Shieh, Minghuey ; Tsai, Hui-Lien. / Mixed-valence tetra- and hexanuclear manganese complexes from the flexibility of pyridine-containing β-diketone ligands. In: Inorganic Chemistry. 2008 ; Vol. 47, No. 6. pp. 1925-1939.
@article{52e6d86031f94a59a25caf242a1017d5,
title = "Mixed-valence tetra- and hexanuclear manganese complexes from the flexibility of pyridine-containing β-diketone ligands",
abstract = "The reactions of [Mn3O(O2CCCl3) 6(H2O)3] with 1-phenyl-3-(2-pyridyl)propane-1, 3-dione (HL1) and 1-(2-pyridly)-3-(p-tolyl)propane-1,3-dione (HL 2) in CH2Cl2 afford the mixed-valence Mn II2MnIII2 tetranuclear complexes [Mn4O-(O2CCCl3)6(L1) 2] (1) and [Mn4O(O2CCCl3) 6L22] (2), respectively. Similar reactions employing [Mn3O(O2CPh)6(H2O)(py) 2] with HL1 and HL2 give the Mn II3MnIII3 hexanuclear complexes [Mn6O2(O2CPh)8(L1) 3] (3) and [Mn6O2(O2CPh) 8L32] (4), respectively. Complexes 1·2CH2Cl2, 2·2CH2Cl 2·H2O, 3·1.5CH2Cl 2·Et2O·H2O, and 4·2CH 2Cl2 crystallize in the triclinic space group P1, monoclinic space group P21/c, monoclinic space group P2 1/n, and monoclinic space group P21/n, respectively. Complexes 1 and 2 consist of a trapped-valence tetranuclear core of [Mn II2MnIII2(μ4-0)] 8+, and complexes 3 and 4 represent a new structural type, possessing a [MnII3MnIII3(μ4-O) 2]11+ core. The magnetic data indicate that complexes 3 and 4 have a ground-state spin value of S = 7/2 with significant magnetoanisotropy as gauged by the D values of -0.51 cm-1 and -0.46 cm-1, respectively, and frequency-dependent out-of-phase signals in alternating current magnetic susceptibility studies indicate their superparamagnetic behavior. In contrast, complexes 1 and 2 are low-spin molecules with an S = 1 ground state. Single-molecule magnetism behavior confirmed for 3 the presence of sweep-rate and temperature-dependent hysteresis loops in single-crystal M versus H studies at temperatures down to 40 mK.",
author = "Yang, {Chen I.} and Wolfgang Wernsdorfer and Tsai, {Yu Jhe} and George Chung and Kuo, {Ting Shen} and Lee, {Gene Hsiang} and Minghuey Shieh and Hui-Lien Tsai",
year = "2008",
month = "3",
day = "17",
doi = "10.1021/ic7013368",
language = "English",
volume = "47",
pages = "1925--1939",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "6",

}

Mixed-valence tetra- and hexanuclear manganese complexes from the flexibility of pyridine-containing β-diketone ligands. / Yang, Chen I.; Wernsdorfer, Wolfgang; Tsai, Yu Jhe; Chung, George; Kuo, Ting Shen; Lee, Gene Hsiang; Shieh, Minghuey; Tsai, Hui-Lien.

In: Inorganic Chemistry, Vol. 47, No. 6, 17.03.2008, p. 1925-1939.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Mixed-valence tetra- and hexanuclear manganese complexes from the flexibility of pyridine-containing β-diketone ligands

AU - Yang, Chen I.

AU - Wernsdorfer, Wolfgang

AU - Tsai, Yu Jhe

AU - Chung, George

AU - Kuo, Ting Shen

AU - Lee, Gene Hsiang

AU - Shieh, Minghuey

AU - Tsai, Hui-Lien

PY - 2008/3/17

Y1 - 2008/3/17

N2 - The reactions of [Mn3O(O2CCCl3) 6(H2O)3] with 1-phenyl-3-(2-pyridyl)propane-1, 3-dione (HL1) and 1-(2-pyridly)-3-(p-tolyl)propane-1,3-dione (HL 2) in CH2Cl2 afford the mixed-valence Mn II2MnIII2 tetranuclear complexes [Mn4O-(O2CCCl3)6(L1) 2] (1) and [Mn4O(O2CCCl3) 6L22] (2), respectively. Similar reactions employing [Mn3O(O2CPh)6(H2O)(py) 2] with HL1 and HL2 give the Mn II3MnIII3 hexanuclear complexes [Mn6O2(O2CPh)8(L1) 3] (3) and [Mn6O2(O2CPh) 8L32] (4), respectively. Complexes 1·2CH2Cl2, 2·2CH2Cl 2·H2O, 3·1.5CH2Cl 2·Et2O·H2O, and 4·2CH 2Cl2 crystallize in the triclinic space group P1, monoclinic space group P21/c, monoclinic space group P2 1/n, and monoclinic space group P21/n, respectively. Complexes 1 and 2 consist of a trapped-valence tetranuclear core of [Mn II2MnIII2(μ4-0)] 8+, and complexes 3 and 4 represent a new structural type, possessing a [MnII3MnIII3(μ4-O) 2]11+ core. The magnetic data indicate that complexes 3 and 4 have a ground-state spin value of S = 7/2 with significant magnetoanisotropy as gauged by the D values of -0.51 cm-1 and -0.46 cm-1, respectively, and frequency-dependent out-of-phase signals in alternating current magnetic susceptibility studies indicate their superparamagnetic behavior. In contrast, complexes 1 and 2 are low-spin molecules with an S = 1 ground state. Single-molecule magnetism behavior confirmed for 3 the presence of sweep-rate and temperature-dependent hysteresis loops in single-crystal M versus H studies at temperatures down to 40 mK.

AB - The reactions of [Mn3O(O2CCCl3) 6(H2O)3] with 1-phenyl-3-(2-pyridyl)propane-1, 3-dione (HL1) and 1-(2-pyridly)-3-(p-tolyl)propane-1,3-dione (HL 2) in CH2Cl2 afford the mixed-valence Mn II2MnIII2 tetranuclear complexes [Mn4O-(O2CCCl3)6(L1) 2] (1) and [Mn4O(O2CCCl3) 6L22] (2), respectively. Similar reactions employing [Mn3O(O2CPh)6(H2O)(py) 2] with HL1 and HL2 give the Mn II3MnIII3 hexanuclear complexes [Mn6O2(O2CPh)8(L1) 3] (3) and [Mn6O2(O2CPh) 8L32] (4), respectively. Complexes 1·2CH2Cl2, 2·2CH2Cl 2·H2O, 3·1.5CH2Cl 2·Et2O·H2O, and 4·2CH 2Cl2 crystallize in the triclinic space group P1, monoclinic space group P21/c, monoclinic space group P2 1/n, and monoclinic space group P21/n, respectively. Complexes 1 and 2 consist of a trapped-valence tetranuclear core of [Mn II2MnIII2(μ4-0)] 8+, and complexes 3 and 4 represent a new structural type, possessing a [MnII3MnIII3(μ4-O) 2]11+ core. The magnetic data indicate that complexes 3 and 4 have a ground-state spin value of S = 7/2 with significant magnetoanisotropy as gauged by the D values of -0.51 cm-1 and -0.46 cm-1, respectively, and frequency-dependent out-of-phase signals in alternating current magnetic susceptibility studies indicate their superparamagnetic behavior. In contrast, complexes 1 and 2 are low-spin molecules with an S = 1 ground state. Single-molecule magnetism behavior confirmed for 3 the presence of sweep-rate and temperature-dependent hysteresis loops in single-crystal M versus H studies at temperatures down to 40 mK.

UR - http://www.scopus.com/inward/record.url?scp=42149152192&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=42149152192&partnerID=8YFLogxK

U2 - 10.1021/ic7013368

DO - 10.1021/ic7013368

M3 - Article

C2 - 18290611

AN - SCOPUS:42149152192

VL - 47

SP - 1925

EP - 1939

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 6

ER -