4.7 Article

A rare alb-4,8-Cmce metal-coordination network based on tetrazolate and phosphonate functionalized 1,3,5,7-tetraphenyladamantane

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CRYSTENGCOMM
卷 15, 期 6, 页码 1235-1243

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ROYAL SOC CHEMISTRY
DOI: 10.1039/c2ce26819a

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  1. Alexander von Humboldt foundation [1135450 STP]
  2. DFG [Ja466/25-1]

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Symmetric tetrahedral ligands are prominent, but somewhat under-investigated building blocks for the generation of coordination polymeric networks. Coordination networks [Mn5Cl2(L-1)2(H2O)(4)(DMF)(4)]center dot 3H(2)O center dot 7DMF, 1 and the [La-2(H5L2)(2)(H2O)(6)], 2 are synthesized under mild solvothermal methods in DMF from the adamantane-based tetrahedral ligands, 1,3,5,7-tetrakis(4-phenyltetrazol-5-yl)adamantane (H4L1), reported for the first time, and 1,3,5,7-tetrakis(4-phenylphosphonic acid) adamantane (H8L2), respectively. Compounds 1 and 2 are based on completely different pentanuclear and binuclear secondary metal building units, respectively, and have different symmetries, but demonstrate an interesting coincidence of underlying topologies, which could be interpreted as a directing or 'imprinting' effect of the symmetry of the rigid tetrahedral ligands. Both structures represent examples of a rarely observed (4,8)-coordinated net. The chi T-M product for 1 at room temperature is slightly lower than the expected for five Mn(II) ions with S = 5/2 and g approximate to 1.98 and on lowering the temperature chi T-M approaches the expected value for a single Mn(II) as a result of the antiferromagnetic coupling through the tetrazolate bridges.

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