Construction And Properties Research Of Octacyano Bridged Mn (?) Molecular Magnet

In recent years, molecular magnets have become a hot topic to scientists because of its unique structure and related properties. Meantime, the design and construction of new supramolecular coordination compounds based on octacyanometalate [M(CN)8]3-/4-(M= Mo? W or Nb) building blocks of potential utility as functional materials has received considerable attention over the recent years. The research in this field has resulted in the cyano-bridged polynuclear octacyanometalate-based molecules and polymeric coordination networks which behave like molecular magnets and photo-induced magnetic materials. In this article, seven new hetero-bimetallic coordination polymers have been synthesized by self-assembly of octacyanometalate building blocks [M(CN)s]3-/4-(M= Mo?W), nitrogen-containing organic ligands and paramagnetic metal ion Mn which have a high spin state. Their structure and magnetic properties have been characterized.1. Two new OD octacyanometalate-based hetero-bimetallic trinuclear complexes were synthesized via rational assembly of building blocks (But4N)3M(CN)8·4H2O (M= Mo, W) with pentadentate gand 2-(pyridin-2-yl)-N1, N3-bis(pyridin-2-ylmethyl)propane-1,3-diamine and manganese perchlorate; one new OD octacyanometalate-based hetero-bimetallic trinuclear complexes was synthesized via rational assembly of building blocks (But4N)3W(CN)8·4H2O with bidentate ligand 5,5'-dimethyl-2,2'-bipyridine and manganese perchlorate. Magnetic measurements show that, in the compounds 1-3, neighboring manganese ions exhibited a weak antiferromagnetic interactions through a diamagnetic NC-MIV-CN bridge.2. Three new 3D network frameworks 4-6 were synthesized via rational assembly of building blocks (But4N)3M(CN)8·4H2O (M= Mo, W) with bidentate ligand 1,4-bis(1-imidazolyl)benzen,4,4'-azo-pyridine and manganese perchlorate; a new one-dimensional infinite 3,2-chain complex was synthesized via rational assembly of building blocks (But4N)3W(CN)8·4H2O with bidentate ligand 4,4'-dimethyl-2,2'-bipyridine and manganese perchlorate. The compound 4 exhibits weak antiferromagnetic coupling between neighboring manganese ions; in contrast, the magnetic behavior of 5,6 is dominated by antiferromagnetic coupling between Mn(?) and M(V) (M= Mo, W) ions; in the one-dimensional chain 7, the neighboring Mn(II)-W(V) shows ferromagnetic coupling.