In search of molecules displaying ferromagnetic exchange: multiple-decker Ni12 and Ni16 complexes from the use of pyridine-2-amidoxime

Abstract

The use of pyridine-2-amidoxime (pyaoxH₂) in Ni chemistry has provided access to a dodecanuclear complex and a hexadecanuclear Ni cluster, namely [Ni₁₂(pyaox)₆(pyaoxH)₆(MeOH)₂Cl₂]Cl₄·5MeOH (1·5MeOH) and [Ni₁₆(pyaox)₈(pyaoxH)₈(MeOH)₄](SO₄)₄·10H₂O·26MeOH (2·10H₂O·26MeOH). Complex 1·5MeOH was isolated by the reaction of NiCl₂·6H₂O, pyaoxH₂ and NaOMe in a 1 : 1 : 2 molar ratio in MeOH in 60% yield. Treatment of NiSO₄·6H₂O with pyaoxH₂ and NEt₃ in a 1 : 1 : 2 molar ratio in MeOH afforded 2·10H₂O·26MeOH in good yield (65%). The two compounds display a multi-decker configuration based on stacked Ni₄ layers, {Ni₄(pyaox)₂(pyaoxH)₂}²⁺_x (x = 3, 1·5MeOH; x = 4, 2·10H₂O·26MeOH); each deck consists of two square planar and two octahedral Ni^II centres. The number of decks observed in 1·5MeOH and 2·10H₂O·26MeOH depends on the nature of the inorganic anion that is present in the reaction system, which provides elements of synthetic control towards new high nuclearity Ni^II species. 2·10H₂O·26MeOH is the first structurally characterized complex of any metal displaying a quadruple-decker configuration, being also the highest nuclearity metal cluster bearing pyaoxH₂ and the highest nuclearity Ni^II cluster with any type of 2-pyridyl oxime. Each cluster cation displays ferromagnetic exchange between the octahedral Ni^II ions resulting in a spin ground state of S = 6 for 1 and S = 8 for 2. Magnetothermal studies have been performed and discussed for both clusters.