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See the Supporting Information
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See the Supporting Information.
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55049094513
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The reaction of K[Co(L-pen)2] with 2 molar equiv of CuCl 2 also produced X-ray-quality crystals of [Cu7(μ 3-OH)6(μ3-Cl)2(L-pends) 3, 1′, 8] whereas the reaction using a mixture of K[Co(D-pen)2] and K[Co(L-pen)2] gave only an unidentified blue precipitate
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2] gave only an unidentified blue precipitate.
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55049140806
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[8]
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[8]
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[8]
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The experimental magnetic data were analyzed using the spin Hamiltonian H, 2J1,(S1S2+S1S 9)-2J2(S1S3+S1S 4+S1S6+SS7)-2J3(S 2S3 +S2S4+S5S 6+S5S7)-2J4(S3S 4+S6S7, 18] based on four magnetic interactions (J1, J2, J3, and J4) between CuII centers; the two cubanes shared by the inner Cu II atom were regarded to be equivalent.[8] The most reliable parameter sets obtained from this analysis; 1: g=2.03, J 1, 0.9, J2=-20.9, J3, 4.1, J 4=-24.0 cm-1; 2: g, 2.06, J1, 1.1, J 2, 20.9, J3, 4.7, J4
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[8]
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34
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55049135549
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[4a,b] and the spin density is symmetrically located on the trimer unit. On the other hand, in 1 the spin density is dominantly located on one of outer Cu atom, representing a unique, quite unsymmetrical magnetic structure. This result, obtained by the DFT calculations, will be reported elsewhere.
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[4a,b] and the spin density is symmetrically located on the trimer unit. On the other hand, in 1 the spin density is dominantly located on one of outer Cu atom, representing a unique, quite unsymmetrical magnetic structure. This result, obtained by the DFT calculations, will be reported elsewhere.
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36
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55049092993
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The detailed mechanism of this reaction is not clear at present, but it is considered that a thiolato-bridged CoIII(D-pen)2Cu II species created at the first stage undergoes an intramolecular redox reaction to be converted into a CoII(D-pends)CuI species, followed by the dissociation of CoII and the auto-oxidation of CuI to give polycopper(II) compounds with N,O-chelating D-pends ligands. The formation of a thiolato-bridged CoIII(D-pen) 2CuII species was indicated by stopped-flow absorption spectroscopy, and the presence of dissociated CoII ions in the reaction solution was confirmed by cation-exchange (SP-Sephadex C-25) column chromatography
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II ions in the reaction solution was confirmed by cation-exchange (SP-Sephadex C-25) column chromatography.
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