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

Complexes of new Schiff base ligands generated in situ from the reaction of 1‐aminoglycerol, aldehydes, and metal ions are reported. [Cu 4 (HL 1 ) 4 ] ( 1 ) and [Ni 4 O(HL 1 ) 3 (H 2 O) 3 )] ⋅ 6 H 2 O ⋅ DMF ⋅ DMSO ( 2 ) have M 4 O 4 cubane cores, with the L/M molar ratios of 4:4 and 3:4, respectively. [Mn III 3 Mn II NaOCl 4 (HL 1 ) 3 ] ⋅ 3  M eCN ( 3 ) has a unique pentanuclear trigonal propeller‐shaped Mn III 3 Mn II Na core structure, and the coordination assemblies are linked by hydrogen bonds to afford a 3D channel structure. [Cu 2 (HL 2 ) 2 ] ( 4 ) has a bis(μ 2 ‐alkoxo)‐bridged Cu 2 O 2 core, with the binuclear species linked by hydrogen bonds to afford a 1D double‐chain. [Ni 7 (OH) 2 (OCH 3 ) 4 (H 2 L 3 ) 2 (MeOH) 2 (H 2 O) 2 ]‐ (ClO 4 ) 2 ⋅ 10 H 2 O ( 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@Ni 6 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.