A Nanosized {NiII 18} Cluster with a 'Flying Saucer' Topology Exhibiting Slow Relaxation of Magnetisation Phenomena at Both 15 K and 1.3 K

Chemistry. 2024 Nov 13:e202403462. doi: 10.1002/chem.202403462. Online ahead of print.

Abstract

A high-nuclearity {Ni18} complex (1) with a unique 'flying saucer' motif has been prepared from the organic chelate, α-methyl-2-pyridine-methanol (mpmH), in conjunction with bridging azido (N3 -) and peroxido (O2 2-) ligands. Magnetic susceptibility measurements revealed the presence of both ferro- and antiferromagnetic exchange interactions between the metal centres in 1, and the stabilization of spin states with appreciable S values at two different temperature regimes. The end-on bridging azido and alkoxido groups are in all likelihood the ferromagnetic mediators, while the η336-bridging peroxides most likely promote the antiparallel alignment of the metals' spin vectors, yielding an overall non-zero spin ground state for the centrosymmetric compound 1. Furthermore, the {Ni18} nanosized cluster behaves as a single-molecule magnet, exhibiting magnetic hysteresis at low temperatures and two relaxation processes at 15 K and 1.3 K, a very rare phenomenon in polynuclear magnetic 3d-metal clusters.

Keywords: coordination clusters; nickel; relaxation of magnetization; single-molecule magnets; structural chemistry.