4.7 Article

A 2D homochiral inorganic-organic framework exhibiting a spin-flop transition

期刊

DALTON TRANSACTIONS
卷 40, 期 27, 页码 7147-7152

出版社

ROYAL SOC CHEMISTRY
DOI: 10.1039/c0dt01686a

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资金

  1. European Research Council
  2. Oppenheimer Fund
  3. National Science Foundation through the Materials World Network [NSF-DMR 0909180, NSF-DMR0520415]

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A 2D homochiral inorganic organic framework {[Mn(NPTA)(4,4'-bpy)(H(2)O)]center dot(H(2)O)(2)}(n) was prepared by assembling achiral polar 4-nitrophthalic acid, manganese ions, and ancillary 4,4'-bipyridine ligands (NPTA = 4-nitrophthalate) (4,4'-bpy = 4,4'-bipyridine). The isomorphous Zn(II) compound was also prepared as a diamagnetic analogue. Adjacent manganese spin centres are linked by the syn-anti carboxylate to form a helical chain, and chains of the same chirality are connected by 4,4'-bpy ligands to generate a homochiral layered framework. Edge-to-face aromatic interactions between neighboring layers lead to a 3D homochiral supramolecular structure. Magnetization and heat capacity measurements indicate that the framework is a weak antiferromagnet at low applied field. The magnetic interactions between adjacent manganese ions in the helical chain can be fitted using the 1D Fisher model, with 2J/k = -0.68 K and g = 2.00. Moreover, the compound displays a unique field-dependent spin flop transition in high magnetic fields, with a critical field of 23.6 kOe at 1.9 K.

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