Polynuclear Complexes with Alkoxo and Phenoxo Bridges from In Situ Generated Hydroxy‐Rich Schiff Base Ligands: Syntheses, Structures, and Magnetic Properties

Abstract

Complexes of new Schiff base ligands generated in situ from the reaction of 1-aminoglycerol, aldehydes, and metal ions are reported. [Cu4(HL(1))4] (1) and [Ni4O(HL(1))3(H2O)3)]⋅6 H2O⋅DMF⋅DMSO (2) have M4O4 cubane cores, with the L/M molar ratios of 4:4 and 3:4, respectively. [Mn(III)3Mn(II)NaOCl4(HL(1))3]⋅3 MeCN (3) has a unique pentanuclear trigonal propeller-shaped Mn(III)3Mn(II)Na core structure, and the coordination assemblies are linked by hydrogen bonds to afford a 3D channel structure. [Cu2(HL(2))2] (4) has a bis(μ2-alkoxo)-bridged Cu2O2 core, with the binuclear species linked by hydrogen bonds to afford a 1D double-chain. [Ni7(OH)2(OCH3)4(H2L(3)2(MeOH)2(H2O)2]-(ClO4)2⋅10 H2O (5) has a heptanuclear structure containing heptadentate di-Schiff base ligands, with the nickel(II) ions bridged by phenoxo, alkoxo, hydroxo, and methoxo groups to afford a very rare face-sharing hexadruple defective cubane core with a Ni@Ni6 arrangement. The lattice water molecules are linked by hydrogen bonds to form helical chains, which are further hydrogen-bonded to the coordination moieties to afford a 2D network. Variable temperature magnetic susceptibility measurements and nonlinear data-fitting revealed that the "2+4" type of cubane complex 1 shows medium intradimeric ferromagnetic interactions and weak interdimeric ferromagnetic interactions. For complexes 2 and 5, coexistent ferro- and antiferromagnetic couplings afford a non-zero spin ground state. However, compound 3 shows antiferromagnetic interactions between Mn(III) and Mn(II) , and ferromagnetic interactions between the Mn(III) centers, resulting in a global antiferromagnetic behavior. In conclusion, the reaction of 1-aminoglycerol with aldehydes and metal salts afforded polynuclear complexes with a rich structural diversity and remarkable magnetic behavior.