Self-assembly of Ni(II) metallacycles (a square and a triangle) supported by tetrazine radical bridges

Two Ni(II) molecular metallacycles of [Ni₄(bpz*tz˙^-)₄(N₃)₄] (1) and [Ni₃(bpz^Phtz˙^-)₃(pz^Ph(Cl)tz˙^-)₃]·1.3CH₃OH·9.3H₂O (2) (bpz*tz = 3,6-bis(3,5-dimethyl-pyrazolyl)-1,2,4,5-tetrazine; bpz^Phtz = 3,6-bis(3-phenyl-pyrazolyl)-1,2,4,5-tetrazine; and pz^Ph(Cl)tz = 3-bis(3-phenyl-pyrazolyl)-6-Cl-1,2,4,5-tetrazine) are reported. The single-crystal X-ray diffraction study reveals that 1 displays a square structure while 2 shows a triangle structure due to the steric effect, both bearing tetrazine radical bridges. Furthermore, magnetic studies reveal that the Ni-radical interaction in 1 is strongly ferromagnetic with a coupling constant (J) of 90.8 cm^-1 in the 2J formalist, while the overall antiferromagnetic behaviour of 2 is presumably due to the compete ferromagnetic (for the Ni-radical_bridging interaction with J₁ = 95.4 cm^-1) and antiferromagnetic (for the Ni-radical_terminal interaction, J₂ = -57.5 cm^-1) couplings.