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One-dimensional (1D) oxalate-bridged homometallic {[Mn(bpy)(C 2 O 4 )]·1.5H 2 O}  n  ( 1 ) (bpy = 2,2'-bipyridine) and heterodimetallic {[CrCu 3 (bpy) 3 (CH 3 OH)(H 2 O)(C 2 O 4 ) 4 ][Cu(bpy)Cr(C 2 O 4 ) 3 ]·CH 2 Cl 2 ·CH 3 OH·H 2 O}  n  ( 2 ) coordination polymers, as well as the three-dimensional (3D) heterotrimetallic {[CaCr 2 Cu 2 (phen) 4 (C 2 O 4 ) 6 ]·4CH 3 CN·2H 2 O}  n  ( 3 ) (1,10-phenanthroline) network, have been synthesized by a building block approach using a layering technique, and characterized by single-crystal X-ray diffraction, infrared (IR) and impedance spectroscopies and magnetization measurements. During the crystallization process partial decomposition of the tris(oxalate)chromate(III) happened and 1D polymers 1 and 2 were formed. The antiferromagnetic interactions between the manganese(II) ions was mediated by oxalate ligands in the chain [Mn(bpy)(C 2 O 4 )]  n  of 1 , with intra-chain super-exchange interaction ? = (-3.134 ± 0.004) K; magnetic interaction between neighbouring chains is negligible making this system closer than other known Mn-chains to the ideal 1D Heisenberg antiferromagnet. Compound 2 comprises a 1D coordination anion [Cu(bpy)Cr(C 2 O 4 ) 3 ]  n  n   - ( Cr2-Cu4 ) with alternating [Cr(C 2 O 4 ) 3 ] 3   -  and [Cu(bpy)] 2+ units mutually bridged through the oxalate group. Another chain ( Cr1-Cu3 ) is similar, but involves a homodinuclear unit [Cu(bpy)(H 2 O)( µ -C 2 O 4 )Cu(bpy)(CH 3 OH)] 2+ ( Cu1-Cu2 ) coordinated as a pendant group to a terminal oxalate oxygen. Magnetic measurements showed that the Cu1  -  Cu2 cationic unit is a strongly coupled antiferromagnetic dimer, independent from the other magnetic ions within ferromagnetic chains Cr1-Cu3 and Cr2-Cu4 . A 3D polymer {[CaCr 2 Cu 2 (phen) 4 (C 2 O 4 ) 6 ]·4CH 3 CN·2H 2 O}  n  ( 3 ) comprising three different metal centers (Ca 2+ , Cr 3+ and Cu 2+ ) oxalate-bridged, contains Ca 2+ atoms as nodes connected with four Cr 3+ atoms through oxalate ligands. The network thus formed can be reduced to an underlying graph of diamondoid ( dia ) or (6 6 ) topology. Magnetization of 3 shows the ferromagnetic oxalate-bridged dimers [Cu II Cr III ], whose mutual interaction could possibly originate through the spin polarization of Ca 2+ orbitals. Compounds 1 and 3 exhibit lower electrical conductivity at room temperature (RT) in comparison to compound 2 .

materials

Magnetic and Electrical Behaviors of the Homo- and Heterometallic 1D and 3D Coordination Polymers Based on the Partial Decomposition of the [Cr(C2O4)3]3− Building Block