Synthesis, Structure, and Magnetic Studies of a New Wheel‐Shaped [LiMn<sup>III</sup><sub>6</sub>] Cluster

Yang, Pei‐Pei

doi:10.1002/zaac.201000431

Cited by 5 publications

(3 citation statements)

References 40 publications

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“…Table S3 summarizes the Mn 6 wheels that can be found in the literature so far. Type a compounds are formed by Mn II or Mn III ions with one small monovalent or divalent ion in the center, such as Mn II , Li + , or Na + , that is usually coplanar or very close to the Mn 6 plane (no more than 0.7 Å from it). − It is worth emphasizing that the Mn II or mixed-valence Mn II/III wheels always show a Mn II ion in the center, − while the Mn III 6 wheels show alkaline ions (Na + or Li + ). − Type b mainly comprises Mn IV 6 wheels with one or two large ions in the center, − although a Mn III 6 with a Mn II ion in the center has been reported . It is interesting to note that within the four Mn III 6 wheels reported in the literature, − only one belongs to type b, and in this case, the central ion is Mn II instead of the alkaline ions that type a exhibit.…”

Section: Resultsmentioning

confidence: 99%

“…We herein present the synthesis and crystal structure of two wheels with formula [Mn 6 M 2 O 9 (4- t BuC 6 H 4 COO) 10 (4- t BuC 6 H 4 COOH) 5 ], where M = Ca 2+ ( 1 ) or Sr 2+ ( 2 ). Several compounds with a Mn 6 wheel-like core have been reported in the literature, showing a wide range of combinations of Mn oxidation states and central ions. − These wheels can be classified in two types: (a) those where the Mn ions are linked through two oxo or oxo derivatives and (b) those where the Mn ions are alternately bridged through one and two oxo or oxo derivatives. Type a wheels prove the versatility of these compounds, which include several Mn z 6 M z ′ x moieties, where z is the Mn oxidation state, M z ′ is the central ion with the z ′ oxidation state, and x is 1 or 2.…”

Section: Introductionmentioning

confidence: 99%

“…Type a wheels prove the versatility of these compounds, which include several Mn z 6 M z ′ x moieties, where z is the Mn oxidation state, M z ′ is the central ion with the z ′ oxidation state, and x is 1 or 2. Then these wheels include the compounds with Mn II 6 Mn II , Mn III 6 Na, , and Mn III 6 Li moieties and several mixed-valence compounds with Mn II/III 6 Mn II moieties. − In contrast, most of type b wheels are compounds with Mn IV 6 Ce IV x , and Mn IV 6 Bi III 2 moieties; only one Mn III 6 Mn II wheel has been described . All these compounds are of great interest for inorganic chemists due to their magnetic properties.…”

Section: Introductionmentioning

confidence: 99%

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Magnetic Behavior of Heterometallic Wheels Having a [Mn^IV₆M₂O₉]¹⁰⁺ Core with M = Ca²⁺ and Sr²⁺

Escriche-Tur¹,

Font-Bardı́a²,

Aullón

et al. 2015

Inorg. Chem.

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Two new heterometallic Mn(IV)-M(2+) compounds with formula [Mn6M2O9(4-(t)BuC6H4COO)10(4-(t)BuC6H4COOH)5] (M = Ca(2+) (1), Sr(2+) (2)) have been crystallized. The core of both compounds consists of a planar Mn6 ring, where the Mn(IV) ions are alternatively bridged by (μ3-O)2(μ-RCOO) and (μ4-O)(μ-RCOO)2 ligands, and the two alkaline earth ions are located to both sides of the wheel, linked to the oxo bridges, generating three fused [Mn2M2O4](4+) cuboids. These compounds show a net antiferromagnetic behavior, more important for 2 (Sr(2+)) than for 1 (Ca(2+)). The fitting of the experimental data was performed with the support of DFT calculations, considering four different exchange pathways: two between adjacent Mn(IV) ions (J1 and J2) and two between nonadjacent Mn(IV) ions (J3 and J4). The results of the analysis show that J1 and J2 are of the opposite sign, the ferromagnetic contribution corresponding to the [Mn2(μ4-O)(μ-RCOO)2](4+) unit (J2). The influence of the M(2+) ions in the magnetic behavior is analyzed for 1 and 2 and for three hypothetical models with the structural parameters of 1 containing Mg(2+), Sr(2+) or without the M(2+) ions. In spite of the diamagnetic character of the alkaline earth ions, their influence on the magnetic behavior has been evidenced and correlated with their polarizing effect. Moreover, the magnetic interactions between nonadjacent ions are non-negligible.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Magnetic Behavior of Heterometallic Wheels Having a [Mn^IV₆M₂O₉]¹⁰⁺ Core with M = Ca²⁺ and Sr²⁺

Escriche-Tur¹,

Font-Bardı́a²,

Aullón

et al. 2015

Inorg. Chem.

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Synthesis, Magnetic Properties, and X‐ray Spectroscopy of Divalent Cobalt(II) and Nickel(II) Cubanes [M^II₄(HL²)₄(OAc)₄]

et al. 2015

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Keywords: N,O ligands / Cubanes / Magnetic properties / X-ray absorption spectroscopy / X-ray photoelectron spectroscopyUnder anaerobic conditions, the reactions of cobalt(II) and nickel(II) acetate tetrahydrate with 2,6-pyridinedimethanol (H 2 L 2 , 3) in anhydrous acetonitrile afforded two tetranuclear metal(II) complexes [M II 4 (HL 2 ) 4 (OAc) 4 ] (4; M II = Co 2+ , Ni 2+ ) with a [M 4 (μ 3 -O) 4 ] 4+ cubane core. X-ray structural analyses revealed that both M II cubanes 4a·2CH 3 OH and 4b·2CH 3 OH are isostructural and crystallize in the tetragonal space group I4 1 /acd with eight molecules in the unit cell. In the solid state, the orientation of the cubane cores of 4 and the formation of a 3D framework were controlled by π-π interactions as well as intra-and intermolecular O-H···O hydrogen bonds.

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Synthesis, magnetic properties, and STM spectroscopy of an unprecedented octanuclear chloro-bridged nickel(ii) double cubane

et al. 2012

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Reaction of nickel(II) chloride hexahydrate with N-n-butyldiethanolamine H(2)L (3) in the presence of LiH in anhydrous THF leads to the formation of the unique octanuclear chloro-bridged nickel(II) double cubane [({Ni(II)(4)(μ(3)-OH)Cl(3)(HL)(3)}μ(2)-Cl)(2)] (4) in 57% yield. According to single crystal X-ray structure analysis, complex 4·4CH(2)Cl(2) possesses a [({Ni(4)(μ(3)-OH)(μ(3)-O)(3)(OH)(3)(N)(3)(Cl)(3)}μ(2)-Cl)(2)] core and crystallizes in the monoclinic space group P2(1)/c with a = 18.292(2), b = 19.8972(5), c = 23.295(2) Å, β = 98.408(6)°, V = 8387.3(8) Å(3), and four molecules in the unit cell. The analysis of the SQUID magnetic susceptibility data identified 4 as a weakly coupled dimer (J(1) = 14.5 K, J(2) = -0.6 K) with a ground state of S = 0, resulting from two S = 4 states of each {Ni(4)} subunits. Although complex 4 does not show an ac out-of-phase signal in a zero dc field at temperatures of 1.8 K and higher, low-temperature magnetization measurements revealed that complex 4 is a single-molecule magnet and shows hysteretic magnetization characteristics with typical temperature and sweep-rate dependencies. The eye-catching feature of complex 4 is the presence of two different blocking temperatures (0.9 K around zero field and 1.3 K at higher fields). The origin of this highly unusual behavior can be assigned to the dimer-nature of the interaction between the two S = 4 units. Furthermore STM and current imaging tunnelling spectroscopy (CITS) were performed on aggregates of 4 drop-coated on highly oriented pyrolytic graphite (HOPG) surfaces. CITS measurements show a strong contrast in the area of the nickel centers and a HOMO-LUMO gap of approximately 0.8 V.

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Synthesis, Structure, and Magnetic Studies of a New Wheel‐Shaped [LiMn^III₆] Cluster

Cited by 5 publications

References 40 publications

Magnetic Behavior of Heterometallic Wheels Having a [Mn^IV₆M₂O₉]¹⁰⁺ Core with M = Ca²⁺ and Sr²⁺

Magnetic Behavior of Heterometallic Wheels Having a [Mn^IV₆M₂O₉]¹⁰⁺ Core with M = Ca²⁺ and Sr²⁺

Synthesis, Magnetic Properties, and X‐ray Spectroscopy of Divalent Cobalt(II) and Nickel(II) Cubanes [M^II₄(HL²)₄(OAc)₄]

Synthesis, magnetic properties, and STM spectroscopy of an unprecedented octanuclear chloro-bridged nickel(ii) double cubane

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Synthesis, Structure, and Magnetic Studies of a New Wheel‐Shaped [LiMnIII6] Cluster

Cited by 5 publications

References 40 publications

Magnetic Behavior of Heterometallic Wheels Having a [MnIV6M2O9]10+ Core with M = Ca2+ and Sr2+

Magnetic Behavior of Heterometallic Wheels Having a [MnIV6M2O9]10+ Core with M = Ca2+ and Sr2+

Synthesis, Magnetic Properties, and X‐ray Spectroscopy of Divalent Cobalt(II) and Nickel(II) Cubanes [MII4(HL2)4(OAc)4]

Synthesis, magnetic properties, and STM spectroscopy of an unprecedented octanuclear chloro-bridged nickel(ii) double cubane

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Synthesis, Structure, and Magnetic Studies of a New Wheel‐Shaped [LiMn^III₆] Cluster

Magnetic Behavior of Heterometallic Wheels Having a [Mn^IV₆M₂O₉]¹⁰⁺ Core with M = Ca²⁺ and Sr²⁺

Magnetic Behavior of Heterometallic Wheels Having a [Mn^IV₆M₂O₉]¹⁰⁺ Core with M = Ca²⁺ and Sr²⁺

Synthesis, Magnetic Properties, and X‐ray Spectroscopy of Divalent Cobalt(II) and Nickel(II) Cubanes [M^II₄(HL²)₄(OAc)₄]