Stereo sensitivity of exchange interactions in NiII and CuII heterospin complexes with 5-formylpyrrolyl-substituted nitroxides

Abstract

5-Formylpyrrolyl-substituted nitronyl and imino nitroxide radicals HL1 and HL2 were synthesized. Their solid phases are formed by packing pairs of the molecules. In the {HL1...HL1} pairs, the dominant interaction is the ferromagnetic exchange with J/kB = 8.8 K (Hamiltonian \(H = 2J\left( {\overrightarrow {{s_1}} \overrightarrow {{s_2}} } \right)\)). The ferromagnetic exchange occurs also in the heterospin molecules [Ni(L1)2], [Cu(L1)2], and [Ni(L2)2(MeOH)2]. In the complexes [Ni(L1)2] and [Cu(L1)2], a small change in the mutual orientation of the coordinated ligands has a considerable effect on the value and the sign of the energy of exchange interactions between the unpaired electrons of the metal ion and paramagnetic ligands.