Synthesis, characterization and magnetic studies on mono-, di-, and tri-nuclear Cu(ii) complexes of a new versatile diazine ligand

The synthesis and coordination chemistry of a new open-chain diazine ligand (L4H ) containing bipyridine, oxime and hydrazone functionalities is reported. Reaction of L4H with CuCl ·2H O affords the mononuclear complex [Cu(L4H )Cl ] (1) in which the ligand acts as a neutral tridentate N,N',N'' donor, whereas treatment with a large excess of CuCl ·2H O affords the dinuclear complex [Cu (L4H)Cl (CH OH)(H O)] (2) in which the ligand is singly-deprotonated at the diazine, offering N,N',N'' and N,N' donor sets to two Cu(ii) ions. Reaction with Cu(NO ) ·3H O yields the trinuclear complex, [Cu (L4H) (CH OH) (NO ) ] (3) in which the ligand is again singly deprotonated, but now presents a tetradentate N,N',N'',N'''-donor set to the first Cu(ii) and behaves as an N,O-chelate to a second Cu(ii), with a conformational change from cis to trans at the diazine moiety. When the latter reaction is repeated in the presence of a mild base, a second trinuclear complex is isolated, [Cu (L4) (CH CH OH)](NO ) (4) in which both the diazine and oxime functionalities of the ligand are deprotonated which subsequently bridges all three Cu(ii) ions, acting as an N,N',N'' donor to the first Cu(ii), a N,N' donor to a second Cu(ii) (similar to 2) and as a terminal O-donor to a third Cu(ii) ion. The Cu(ii) ions are linked mutually cis via the two-atom diazine bridge in the case of 2 and 4 and trans in the case of 3. Magnetic studies reveal the presence of weak ferromagnetic interactions in 2 (g = 2.2, J/k = +12.8 K) and strong antiferromagnetic interactions in both 3 and 4 (g = 2.093 J/k = -140 K and g = 2.24 J/k = -300 K respectively).