Multiredox Active [3 × 3] Copper Grids

A nonanuclear copper grid complex, [CuII9(L)6]­(BF4)6·1-PrOH·5H2O (1·1-PrOH·5H2O; L = 2,6-bis­[5-(2-pyridinyl)-1H-pyrazol-3-yl]­pyridine), was synthesized with a [3 × 3] grid structure consisting of nine CuII ions and six deprotonated ligands and displayed four-step quasi-reversible redox behavior from [CuII9] to [CuI4CuII5]. The corresponding heterovalent complex [CuI2CuII7(L)6]­(PF6)4·3H2O (2·3H2O) was successfully isolated and had a distorted core structure that radically changed the intramolecular magnetic coupling pathways.