Abstract
Three coordination polymers of metal(II)-dicyanamido (dca) complexes with 4-methoxypyridine-N-oxide (4-MOP-NO); namely, catena-[Co(µ1,5-dca)2(4-MOP-NO)2] (1), catena-[Mn(µ1,5-dca)2(4-MOP-NO)2] (2), catena-[Cd(µ1,5-dca)2(4-MOP-NO)2] (3), and the mononuclear [Cu(κ1dca)2(4-MOP-NO)2] (4), were synthesized in this research. The complexes were analyzed by single crystal X-ray diffraction as well as spectroscopic methods (UV/vis, IR). The polymeric 1-D chains in complexes 1–3 were achieved by the doubly µ1,5-bridging dca ligands and the O-donor atoms of two axial 4-MOP-NO molecules in trans configuration around the distorted M(II) octahedral. On the other hand, the two “trans-axial” pyridine-N-oxide molecules in complexes 2 and 3 display opposite orientation (s-trans). The DFT (density functional theory) computational studies on the complexes 1–3 were consistent with the experimentally observed crystal structures. Compounds 1 and 2 display weak antiferromagnetic coupling between metal ions (J = −10.8 for 1 and −0.35 for 2).
Highlights
The reaction of aqueous solutions of metal(II) nitrates with Nadca and 4-methoxypyridine-N-oxide in 1:2:2 molar ratio resulted in the formation of the polymeric chains catena-[M(μ1,5 -dca)2 (4-MOP-NO)2 ]
In the coordination polymers (CPs) complexes, the polymeric 1D chains were achieved by the doubly μ1,5 -bridging dca ligands and the O-donor atoms of the two axial 4-MOP–NO molecules are in trans configuration around the distorted M(II) octahedral
The trans-orientation adapted in title complexes, 1–3 are very similar to those observed in the corresponding CPs, catena-[M(μ1,5 -dca)2 (L)2 ], where L = 4-hydroxymethylpyridine or 3-aminopyridine and M = Co, Mn, Cu, Zn, or Cd [10,63]
Summary
Small pseudohalide ions such as N3 − , NCS− , NCSe− , and NCO− , as well as the longer dicyanamide ion N(CN)2 − , are known to bind divalent 3d and 4d metal ions in a variety of ways, and have been extensively used as linkers between metal ions and the construction of coordination polymers (CPs) with different nuclearities, frameworks, and topologies [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26]. The bridged pseudohalide complexes have the capability to transmit the magnetic interaction between the paramagnetic metal centers across the bridged pseudohalides [1,2,3,4,5,6,7,8,10,11,12,13,14,18,19,20,21,22,23,24]. The bridged pseudohalide complexes have the capability to transmit the magnetic interaction between the paramagnetic metal centers across the bridged. The dicyanamido complexes display a wide range of coordination modes with divalent metal. Complexes containing pyridine and pyridine-N-oxide derivatives as pseudohalide metal(II) complexes containing pyridine and pyridine-N-oxide derivatives as coligands, coligands, thestudy following study was With undertaken.
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