4.7 Article

Heterobimetallic Tungsten/Molybdenum(IV)-Copper(II) MOFs Constructed by a Unique 2D → 3D Architecture and Exhibiting New Topology and Magnetic Properties

Journal

CRYSTAL GROWTH & DESIGN
Volume 9, Issue 12, Pages 5351-5355

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/cg9008834

Keywords

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Funding

  1. National Natural Science Foundation of China [50925207]
  2. Ministry of Science and Technology of China [2009DFA50620]
  3. Special Fund for International Collaboration & Exchange of Jiangsu Province [BZ2008049]
  4. Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japan

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The present Study describes the designed synthesis, X-ray structures, and magnetic properties of two 3D cyano-bridged heterobimetallic tungsten/molybdenum(IV)-copper(II)MOFs,{[mu(4)-M(CN)(8)]Cu-2(DPP)(4)}(n)(M = W 1, Mo 2; DPP = 1,3-Di(4-pyridyl)propane). Both MOFs 1 and 2 were constructed by interdiffusion approach in two steps: the first reaction of CuSCN and NH4SCN with the flexible bridging ligand DPP in polar solvent for building a 2D homometallic Cu polymer, and the thereafter conformation of 3D heterobimetallic MOF architectures with [M(CN)(8)](3-) and 2D coordination networks. MOFs 1 and 2 are isomorphous and both crystallize in the tetragonal system and have space group l4(1)/a, with unit cell constants a = 19.734(3) angstrom, b = 19.734(3) angstrom, c = 13.989(2) angstrom for 1, and a = 19.7429(19) angstrom, b = 19.7429(19) angstrom, c = 13.9883(15) angstrom for 2. Our study demonstrates that such heterobimetallic MOFs possess a unique 2D -> 3D architecture and exhibit a new 2-nodal topological structure. The magnetic measurement or MOFs shows typical paramagnetic properties and weak ferromagnetic interactions.

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