Cascade complexation: a single cyano bridge links a pair of Cu(II) cations.

A series of structurally characterised mu-cyanodicopper(II) cryptates shows moderately strong antiferromagnetic interaction in the range -2J= 150-200 cm(-1), at the high end of the observed range for such assemblies. The lowest magnetic exchange coupling parameter is displayed where there is slight bending of the M-CN-M assembly, enforced by the constraints of cryptate encapsulation. Thermally accessible triplet EPR spectra are observed with zero-field splittings of the order of 0.13-0.14 cm(-1), confirming collinear ground-state dz2 orbitals for Cu(II), consistent with their trigonal-bipyramidal coordination geometries.