From the {Cu(μ2-S)N}4 butterfly architecture to the {Cu(μ3-S)N}12 double wheel

Begum, Mohammed S. Ameerunisha; Seewald, Oliver; Flörke, Ülrich; Henkel, Gerald

doi:10.1016/j.ica.2007.09.047

“…[8,9] Multiple-stranded wheels are less common and encompass either 1) wheels built from repeating metal clusters, [10] or 2) multiple-layer wheels, that is, complexes that consist of two or more linked parallel wheels. Those of structural type (2) are extremely rare, being restricted to [V 12 ], [11] [Mn 10 ], [12] [Mn 16 ], [13] and [Cu 12 ] [14] double-deckers, [15] none of which display SMM behavior. Herein we report a beautiful new mixed-valent [Mn 32 ] double-decker wheel, which is the highest-nuclearity cluster possessing this topology, and show that it has a large spin ground state and displays SMM behavior with the largest effective barrier to magnetization relaxation (U eff % 44.5 K) for any molecular wheel.…”

mentioning

confidence: 99%

“…The reaction of MnBr 2 ·4 H 2 O, NaO 2 CMe, 2-phenyl-1,2-propanediol (Ph-pdH 2 ), and 2-hydroxyacetophenone oxime (Me-saoH 2 ) in a 1:1:1:1 molar ratio in MeCN leads to the isolation of [Mn 32 (m 4 -O) 8 (m 3 -OH) 6 (Me-sao) 14 [18] charge-balance considerations, and inspection of metric parameters.…”

mentioning

confidence: 99%

A [Mn₃₂] Double‐Decker Wheel

Manoli

¹

,

Inglis

²

,

Manos

³

et al. 2011

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Polynuclear clusters of paramagnetic 3d metal ions continue to attract significant interest because of their intriguing geometrical characteristics (large size, high symmetry, aesthetically pleasing shapes and architectures) and fascinating physical properties. Such complexes often combine large and sometimes abnormally large spin ground states with easyaxis-type magnetic anisotropy, resulting in a significant barrier to magnetization relaxation. [1][2][3] Thus, at sufficiently low temperatures they function as single-domain magnetic particles displaying magnetization hysteresis and quantum tunneling of the magnetization (QTM). [3, 4] Such singlemolecule magnets (SMMs) represent a molecular approach to nanoscale magnetic materials with potential applications in information storage and molecular spintronics.[5] SMMs with nuclearities up to 84 and structural topologies as diverse as (amongst others) dimers, triangles, cubanes, tetrahedra, icosahedra, and wheels are now known. [1][2][3]6] The latter of these have always attracted intense interest, partly because of their inherent structural beauty, but also because they represent model systems for the study of one-dimensional magnetism, spin frustration, and quantum effects and are promising candidates for use as qubits in quantum computation.[7] Homo-and heterometallic molecular wheels are commonly encountered in 3d cluster chemistry, [8][9][10][11][12][13][14][15] and in general they fall into two distinct structural types. By far the most common are single-stranded wheels, which simply describe linked monometallic units. [8, 9] Multiple-stranded wheels are less common and encompass either 1) wheels built from repeating metal clusters, [10] or 2) multiple-layer wheels, that is, complexes that consist of two or more linked parallel wheels. Those of structural type (2) are extremely rare, being restricted to [V 12 (Figure 1 a) (Figure 1 b, (Figure 1 c) [18] charge-balance considerations, and inspection of metric parameters.The metal-oxygen core of the cluster consists of four pairs of edge-sharing {M 4 O} tetrahedra situated at the "corners" of

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“…[1][2][3]6] The latter of these have always attracted intense interest, partly because of their inherent structural beauty, but also because they represent model systems for the study of one-dimensional magnetism, spin frustration, and quantum effects and are promising candidates for use as qubits in quantum computation. [7] Homo-and heterometallic molecular wheels are commonly encountered in 3d cluster chemistry, [8][9][10][11][12][13][14][15] and in general they fall into two distinct structural types. By far the most common are single-stranded wheels, which simply describe linked monometallic units.…”

mentioning

confidence: 99%

“…[8, 9] Multiple-stranded wheels are less common and encompass either 1) wheels built from repeating metal clusters, [10] or 2) multiple-layer wheels, that is, complexes that consist of two or more linked parallel wheels. Those of structural type (2) are extremely rare, being restricted to [V 12 ], [11] [Mn 10 ], [12] [Mn 16 ], [13] and [Cu 12 ] [14] double-deckers, [15] none of which display SMM behavior. Herein we report a beautiful new mixed-valent [Mn 32 ] double-decker wheel, which is the highest-nuclearity cluster possessing this topology, and show that it has a large spin ground state and displays SMM behavior with the largest effective barrier to magnetization relaxation (U eff % 44.5 K) for any molecular wheel.…”

mentioning

confidence: 99%

“…The reaction of MnBr 2 ·4 H 2 O, NaO 2 CMe, 2-phenyl-1,2propanediol (Ph-pdH 2 ), and 2-hydroxyacetophenone oxime (Me-saoH 2 ) in a 1:1:1:1 molar ratio in MeCN leads to the isolation of [Mn 32 (m 4 -O) 8 (m 3 -OH) 6 (Me-sao) 14 (O 2 CMe) 18 Br 8 -(H 2 O) 10 ](OH) 2 (1) in 30 % yield after approximately 1 week. The diol does not appear in the final product, but its presence in the reaction mixture is essential, since reactions in its absence lead to the formation of a known [Mn 7 ] cluster.…”

mentioning

confidence: 99%

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A [Mn₃₂] Double‐Decker Wheel

Manoli¹,

Inglis²,

Manos³

et al. 2011

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Polynuclear clusters of paramagnetic 3d metal ions continue to attract significant interest because of their intriguing geometrical characteristics (large size, high symmetry, aesthetically pleasing shapes and architectures) and fascinating physical properties. Such complexes often combine large and sometimes abnormally large spin ground states with easyaxis-type magnetic anisotropy, resulting in a significant barrier to magnetization relaxation. [1][2][3] Thus, at sufficiently low temperatures they function as single-domain magnetic particles displaying magnetization hysteresis and quantum tunneling of the magnetization (QTM). [3, 4] Such singlemolecule magnets (SMMs) represent a molecular approach to nanoscale magnetic materials with potential applications in information storage and molecular spintronics. [5] SMMs with nuclearities up to 84 and structural topologies as diverse as (amongst others) dimers, triangles, cubanes, tetrahedra, icosahedra, and wheels are now known. [1][2][3]6] The latter of these have always attracted intense interest, partly because of their inherent structural beauty, but also because they represent model systems for the study of one-dimensional magnetism, spin frustration, and quantum effects and are promising candidates for use as qubits in quantum computation. [7] Homo-and heterometallic molecular wheels are commonly encountered in 3d cluster chemistry, [8][9][10][11][12][13][14][15] and in general they fall into two distinct structural types. By far the most common are single-stranded wheels, which simply describe linked monometallic units. [8, 9] Multiple-stranded wheels are less common and encompass either 1) wheels built from repeating metal clusters, [10] or 2) multiple-layer wheels, that is, complexes that consist of two or more linked parallel wheels. Those of structural type (2) are extremely rare, being restricted to [V 12 ], [11] [Mn 10 ], [12] [Mn 16 ], [13] and [Cu 12 ] [14] double-deckers, [15] none of which display SMM behavior. Herein we report a beautiful new mixed-valent [Mn 32 ] double-decker wheel, which is the highest-nuclearity cluster possessing this topology, and show that it has a large spin ground state and displays SMM behavior with the largest effective barrier to magnetization relaxation (U eff % 44.5 K) for any molecular wheel.The reaction of MnBr 2 ·4 H 2 O, NaO 2 CMe, 2-phenyl-1,2propanediol (Ph-pdH 2 ), and 2-hydroxyacetophenone oxime (Me-saoH 2 ) in a 1:1:1:1 molar ratio in MeCN leads to the isolation of [Mn 32 (m 4 -O) 8 (m 3 -OH) 6 (Me-sao) 14 (O 2 CMe) 18 Br 8 -(H 2 O) 10 ](OH) 2 (1) in 30 % yield after approximately 1 week. The diol does not appear in the final product, but its presence in the reaction mixture is essential, since reactions in its absence lead to the formation of a known [Mn 7 ] cluster. [16] The structure of the cation of 1 [17] reveals it to be a centrosymmetric, mixed-valent [Mn II 18 Mn III 14 ] doubledecker wheel (Figure 1 a), consisting of two linked, parallel [Mn II 7 Mn III 7 ] crown-shaped wheels (Figure 1 b, c) th...

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The Chemistry of Metal Thiophenolates

Klingele¹,

Kersting²

2013

Patai's Chemistry of Functional Groups

0

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The present article reviews structures, properties, reactivity and applications of transition metal complexes supported by the parent thiophenolate ligand system and various derivatives thereof. This extensive outline of literature published in the last decade covers publications about di‐ and higher nuclear complexes that exhibit bridging thiophenolate functions. The structuring of this contribution is based on the type of ligand involved in the coordination, covering monodentate thiophenolate ligands as well as bi‐ and higher dentate derivatives being acyclic or macrocyclic. An emphasis is set on structures but reactions, reactivity and catalysis, redox chemistry, and other properties of the complexes in review are discussed where appropriate.

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From the {Cu(μ2-S)N}4 butterfly architecture to the {Cu(μ3-S)N}12 double wheel

Cited by 9 publications

References 18 publications

A [Mn₃₂] Double‐Decker Wheel

A [Mn₃₂] Double‐Decker Wheel

A [Mn₃₂] Double‐Decker Wheel

The Chemistry of Metal Thiophenolates

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From the {Cu(μ2-S)N}4 butterfly architecture to the {Cu(μ3-S)N}12 double wheel

Cited by 9 publications

References 18 publications

A [Mn32] Double‐Decker Wheel

A [Mn32] Double‐Decker Wheel

A [Mn32] Double‐Decker Wheel

The Chemistry of Metal Thiophenolates

Contact Info

Product

Resources

About

A [Mn₃₂] Double‐Decker Wheel

A [Mn₃₂] Double‐Decker Wheel

A [Mn₃₂] Double‐Decker Wheel