| Summary: | Complex formation of nickel(II) tetrafluoroborate and <i>tert</i>-butyl 5-phenyl-2-pyridyl nitroxide (phpyNO) in the presence of sodium cyanate gave a discrete molecule [Ni(phpyNO)<sub>2</sub>(X)<sub>2</sub>] (X = NCO). The Ni-O-N-C<sub>sp</sub>2 torsion angles were reduced on heating; 33.5(5)° and 36.2(4)° at 100 K vs. 25.7(10)° and 32.3(11)° at 400 K. The magnetic behavior was almost diamagnetic below ca. 100 K, and the <i>χ</i><sub>m</sub><i>T</i> value reached 1.04 cm<sup>3</sup> K mol<sup>−1</sup> at 400 K. An analysis using the van’t Hoff equation indicates a possible spin transition at <i>T</i><sub>1/2</sub> >> 400 K. Density functional theory calculation shows that the singlet-quintet energy gap decreases as the structural change from 100 to 400 K. The geometry optimization results suggest that the diamagnetic state has the Ni-O-N-C<sub>sp</sub>2 torsion angles of 32.7° while the <i>S</i><sub>total</sub> = 2 state has those of 11.9°. The latter could not be experimentally observed even at 400 K. After overviewing the results on the known X = Br, Cl, and NCS derivatives, the magnetic behavior is described in a common phase diagram. The Br and Cl compounds undergo the energy level crossing of the high-/low-spin states, but the NCS and NCO compounds do not in a conventional experimental temperature range. The spin transition mechanism in this series involves the exchange coupling switch between ferro- and antiferromagnetic interactions, corresponding to the high- and low-spin phases, respectively.
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