Strong Exchange Coupling in a Trimetallic Radical‐Bridged Cobalt(II)‐Hexaazatrinaphthylene Complex

Reducing hexaazatrinaphthylene (HAN) with potassium in the presence of 18-c-6 produces [{K(18-c-6)}HAN], which contains the S=1/2 radical [HAN](.-) . The [HAN](.-) radical can be transferred to the cobalt(II) amide [Co{N(SiMe3 )2 }2 ], forming [K(18-c-6)][(HAN){Co(N'')2 }3 ]; magnetic measurements on this compound reveal an S=4 spin system with strong cobalt-ligand antiferromagnetic exchange and J≈-290 cm(-1) (-2 J formalism). In contrast, the Co(II) centres in the unreduced analogue [(HAN){Co(N'')2 }3 ] are weakly coupled (J≈-4.4 cm(-1) ). The finding that [HAN](.-) can be synthesized as a stable salt and transferred to cobalt introduces potential new routes to magnetic materials based on strongly coupled, triangular HAN building blocks.