Cyclic M2(RL)2 coordination complexes of 5-(3-[N-tert-butyl-N-aminoxyl]phenyl)pyrimidine with paramagnetic transition metal dications

5-(3-(N-tert-Butyl-N-aminoxyl)phenyl)pyrimidine (RL = 3NITPhPyrim) forms isostructural Cyclic M-2(RL)(2) cyclic dimers with M-2(hfac)(2) (M = Mn, Co, Cu; hfac = hexafluoroacetylaceton ate). Mn-2(hfaC)(4)(RL)(2) exhibits strong antiferromagnetic Mn-RL exchange, with weak ferromagnetic exchange (0.7 cm(-1)) between Mn-RL units that is consistent with a spin polarization exchange mechanism. The magnetic moment Of Co-2(hfac)(4)(RL)(2) at higher temperatures is consistent with strongly antiferromagnetic exchange within the Co-NIT units and tends toward zero below 50 K at lower magnetic fields, Cu-2(hfac)(4)(RL)(2) shows more complex behavior, with no high-temperature plateau in XT(T) up to 300 K but a monotonic decrease down to about 100 K. The Cu(II)-nitroxide bonds decrease by 0.2-0.3 angstrom over the same temperature range, corresponding to a change of nitroxide coordination from axial to equatorial. This thermally reversible Jahn-Teller distortion leads to a thermally induced spin state conversion from a high-spin, paramagnetic state at higher temperature to a low-spin state at lower temperature, This spin state conversion is accompanied by a reversible solid-state thermochromic change between dull yellow-brown at room temperature and green at 77 K.