Hexanuclear Copper(II) Cages Built on a Central {μ3-O•••H•••μ3-O} Moiety, 1,3-Bis(dimethylamino)-2-propanolato and Capping R-phosphonates: Crystal Structures, Magnetic Behavior, and DFT Studies

The syntheses, structural characterization, and magnetic behavior of two new hexanuclear copper(II) complexes derived from R-phosphonic acids and 1,3-bis(dimethylamino)-2-propanol (Hbdmap) with formulas [Cu-6(mu-bdmap)(3)(mu(3)-Ph-PO3)(2) (mu(3)-O center dot center dot center dot H center dot center dot center dot mu(3)-O)(ClO4)(2)(H2O)]center dot 5H(2)O (1) and [Cu-6(mu-bdmap)(3)(mu(3)-t-Bu-PO3)(2)(mu(3)-O center dot center dot center dot H center dot center dot center dot mu(3)-O)(mu(1,3)-dca)(dca)-(H2O)]center dot 6H(2)O (2) (Ph-H2PO3 = phenylphosphonic acid, t-Bu-H2PO3 = tert-butylphosphonic acid, dca = dicyanamide) are reported. Compounds 1 and 2 are hexanuclear 3.111 R-phosphonate(2-)/1,3-bis(dimethylamino)-2-propanolato(1-) cages including in the center the [mu(3)-O center dot center dot center dot H center dot center dot center dot mu(3)-O](3-) unit. The temperature dependence of the magnetic properties of 1 and 2 clearly indicates an overall strong antiferromagnetic coupling confirmed by DFT calculations.