Antiferromagnetic Mixed-Valence Cu(I)–Cu(II) Two-Dimensional Coordination Polymers Constructed by Double Oximato Bridged Cu(II) Dimers and CuISCN Based One-Dimensional Anionic Chains

Abstract

One dinuclear Cu(II) complex [Cu2L22(EtOH)0.5(ClO4)](ClO4) (1) has been synthesized by reacting an oxime-based tridentate Schiff base ligand, 3-[2-(diethylamino)ethylimino]butan-2-one oxime (HL2), with CuII(ClO4)2, whereas the reaction of another similar ligand, 3-[2-(dimethylamino)ethylimino]butan-2-one oxime (HL1), and this ligand (HL2) with CuII(ClO4)2 in the presence of NaSCN yielded two rare mixed-valence Cu(I)–Cu(II) two-dimensional (2D) coordination polymers, 2∞[{(CuII2L12)}{CuI4(μ1,3-SCN)2(μ1,1,3-SCN)4}]n (2) and 2∞[{(CuII2L22)}{CuI2(μ1,3-SCN)2(μ1,1,3-SCN)2}]n (3), respectively. The presence of SCN– during the synthesis of the complexes induces reduction of a part of the Cu(II) to Cu(I) giving rise to these two novel mixed-valence 2D coordination polymers 2 and 3. All three complexes have been structurally and magnetically characterized. In complex 1, the square pyramidal Cu(II) atoms are joined by the double oximato bridges. On the other hand, the railroad track-like 2D sheet of 2 and stair-like ...