The use of a semi-flexible bipyrimidyl ligand for the construction of azide-based coordination polymers: structural diversities and magnetic properties.

Abstract

Using a semi-flexible quadritopic N-donor ligand, 5,5'-bipyrimidine (bpym), four new azide-based coordination polymers, {[Co2(bpym)(N3)4]·MeCN}n (1), [Co(bpym)(N3)2]n (2), [Mn(bpym)(N3)2]n (3) and {[Ni3(bpym)3(N3)6]·2H2O}n (4) were synthesized and structurally characterized. With bpym aciting as a planar μ4-bridging ligand, the resulting compound, 1, comprised a net-to-net 3D framework composed of two grid-like 44-subnets, Co(EE-N3)2-based and Co2(bpym)-based sheets, with a (4,6)-connected (42·64)(48·66·8)2 topology. Compound 2 adopted a 3D pillared-layer framework with a pts topology based on six-connected Co(ii) centers and four-connected twisted μ4-bpym ligands, while compound 3 adopted a 3D pillared-layer structure with a bcu topology based on Co(EE-N3)2-based 44-layers and two-connected twisted μ2-bpym pillars. In contrast, compound 4 had a 2D layered structure composed of 1D Ni(ii) chains with alternating double EE-N3 and double EO-N3 bridges in an EE-EE-EO sequence and two-connected bpym linkers. The magnetic properties of 1-4 were investigated. The findings indicate that 1 showed weak ferromagnetism due to spin-canted antiferromagnetism and long-range magnetic ordering with a critical temperature, TC = 12.6 K. In contrast, compound 2 exhibited weak ferromagnetism due to spin-canted antiferromagnetism and antiferromagnetic ordering. In compound 3, antiferromagnetic interactions dominated between the Mn(ii) centers through the EE-N3 bridges. In compound 4, the antiferromagnetic and ferromagnetic interactions were transmitted through double EE-N3 and double EO-N3 bridges, respectively, resulting in an AF-AF-F topological ferrimagnetic Ni(ii) chain. Furthermore, field-induced magnetic phase transitions of metamagnetism for 2 and 4 were also observed below TN = 3.6 K and 8.2 K, respectively.