Diverse Structures and Magnetism of Cobalt(II) and Manganese(II) Compounds with Mixed Azido and Carboxylato Bridges Induced by Methylpyridinium Carboxylates

摘要

Herein we present a systematic study of the structures and magnetic properties of six coordination compounds with mixed azide and zwitterionic carboxylate ligands, [M(N₃)₂(2-mpc)] (2-mpc=N-methylpyridinium-2-carboxylate; M=Co for 1 and Mn for 2), [M(N₃)₂(4-mpc)] (4-mpc=N-methylpyridinium-4-carboxylate; M=Co for 3 and Mn for 4), [Co₃(N₃)₆(3-mpc)₂(CH₃OH)₂] (5), and [Mn₃(N₃)₆(3-mpc)₂] (6; 3-mpc=N-methylpyridinium-3-carboxylate). Compounds 1–3 consist of one-dimensional uniform chains with (μ-EO-N₃)₂(μ-COO) triple bridges (EO=end-on); 5 is also a chain compound but with alternating [(μ-EO-N₃)₂(μ-COO)] triple and [(EO-N₃)₂] double bridges; Compound 4 contains two-dimensional layers with alternating [(μ-EO-N₃)₂(μ-COO)] triple, [(μ-EO-N₃)(μ-COO)] double, and (EE-N₃) single bridges (EE=end-to-end); 6 is a layer compound in which chains similar to those in 5 are cross-linked by a μ₃-1,1,3-N₃ azido group. Magnetically, the three CoII compounds (1, 3, and 5) all exhibit intrachain ferromagnetic interactions but show distinct bulk properties: 1 displays relaxation dynamics at very low temperature, 3 is an antiferromagnet with field-induced metamagnetism due to weak antiferromagnetic interchain interactions, and 5 behaves as a noninnocent single-chain magnet influenced by weak antiferromagnetic interchain interactions. The magnetic differences can be related to the interchain interactions through π–π stacking influenced by different substitution positions in the ligands and/or different magnitudes of intrachain coupling. All of the MnII compounds show overall intrachain/intralayer antiferromagnetic interactions. Compound 2 shows the usual one-dimensional antiferromagnetism, whereas 4 and 6 exhibit different weak ferromagnetism due to spin canting below 13.8 and 4.6 K, respectively.