Structural, electronic, and magnetic properties of (Fe[HC(3,5-Me2pz)3]2)(BF4)2 (pz = pyrazolyl): observation of unusual spin-crossover behavior.

The complex {Fe[HC(3,5-Me2pz)3]2}(BF4)2, shown crystallographically to contain a unique octahedral N6Fe site, shows a new type of spin-crossover behavior. The solid is high-spin from 350 K down to a temperature of 206 K, but below 206 K it undergoes a very abrupt decrease in magnetic moment. Mossbauer studies show conclusively that the magnetic moment change observed at 206−200 K arises from the complex changing over a very small temperature range from a high-spin state at higher temperatures to a mixture of high-spin and low-spin at lower temperatures, a mixture that does not change composition as the temperature is lowered to 5 K.