Complex chemistry of 2,2,6,6-tetramethyl-4-(2,2′∶6′,2″-terpyridin-4′-yloxy)piperidin-1-oxyl, a spin-labelled terpyridine‡
Abstract
Reaction of 4′-chloro-2,2′∶6′,2″-terpyridine with 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl in the presence of 4 equivalents of powdered KOH in dmso at 50 °C for 16 h, followed by an aqueous quench, afforded 2,2,6,6-tetramethyl-4-(2,2′∶6′,2″-terpyridin-4′-yloxy)piperidin-1-oxyl (L1) in 70% recrystallised yield. The complexes [ML12][BF4]2 (M = Mn 1, Co 2, Ni 3, Cu 4 or Zn 5) have been prepared and characterised. Crystals of 1 grown from MeCN–Et2O contain octahedral manganese(II) centres, with Mn–N 2.188(3)–2.263(3) Å and Mn· · ·N(aminoxyl) distances of 9.740(4) and 9.530(4) Å. The structure shows an unusual O· · ·O contact between aminoxyl centres on adjacent molecules. Voltammetric measurements of L1 and 1–5 in MeCN–0.1 M NBu4PF6 showed a reversible aminoxyl/oxoammonium oxidation, which is perturbed minimally by complexation; 1–4 also showed complex metal-centred redox behaviour, which for 1–3 differs from that reported for other [M(terpy)2]2+ derivatives of these metal ions. The X- and Q-band EPR spectra of 4 in MeCN–toluene (10∶1) show a broad resonance characteristic of strong Cu/L1 exchange. Variable temperature susceptibility measurements on solid 1 and 4 revealed weakly antiferromagnetic behaviour. Data for 4 can be reproduced by the Curie–Weiss law, and by an equation describing intramolecular superexchange. However, those for 1 show a sharp drop in χmT below 10 K, which cannot be fitted by these models; it is proposed that this reflects the intermolecular O· · ·O contacts in the solid.