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A new chiral 3D heterometallic coordination polymer [NaCo2(L)2(N3)·(MeOH)]∞ (1) (L = 2,6-pyridinedicarboxylate) was synthesized and characterized magnetically. Ferro- and antiferromagnetic interactions co-exist in 1, which results in a magnetic phase transition at the high temperature of 29 K.

The Cu(II) ions usually have different coordinated geometry to other 3d ions, especially Ni(II) and Co(II) ions, in azido-carboxylate mixed ligand systems. That provides a potential way to synthesize rare heterometallic 3d-3d azido complexes with peculiar magnetic properties. Assembling Cu(II), M(II) (M = Ni and Co), azido and nicotinic acid in hydrothermal condition, two novel isomorphic 3D heterometallic 3d-3d azido complexes, [CuM(N(3))(2)(nicotinate)(2)](∞) (M = Ni(II) for 1 and Co(II) for 2) were obtained. The structure of the complexes can be described as EO azido and syn,syn carboxylate mixed bridged spin sequence chains (-1/2-J(1)-1-J(2)-1/2- for 1 and -1/2-J(1)-3/2-J(2)-1/2- for 2) linked by the pyridyl groups. Dominant ferromagnetic interactions were observed between the Cu(II) and M(II) ions in the chains despite the largest M-N-M angle of about 129° in the 3d metal azido-carboxylate mixed coordinated systems and weak antiferromagnetic interactions between the chains. At low temperature, a spin-flop phase transition was present in the Co(II) involved complex 2.

Three new 1D lanthanide-azido complexes, [Ln(2)(N(3))(isonic)(2)-(OH)(3)(Hisonic)(H(2)O)](n) (Ln = Gd(III), Eu(III) and Sm(III)), were synthesized by hydrothermal reaction and their magnetic properties were studied.

A new 3D porous Ni(II)-azido complex has been synthesized and characterized and exhibits guest sorption properties explored by single-crystal to single-crystal transformations and linear ferromagnetic chains held together by a Ni-isonicotinate framework.