Spin Transition of an Iron(II) Organoborate Complex in Different Polymorphs and in Vacuum-Deposited Thin Films: Influence of Cooperativity.

Two polymorphic modifications ( and ) of the new spin crossover (SCO) complex [Fe{HB(pz)(pypz)}] (pz = pyrazole, pypz = pyridylpyrazole; ) were prepared and investigated by differential scanning calorimetry (DSC), magnetic measurements, Mößbauer, vibrational, and absorption spectroscopy as well as single-crystal and X-ray powder diffraction. DSC measurements reveal that upon heating the thermodynamically metastable form to ∼178 °C it transforms into in an exothermic reaction, which proves that these modifications are related by monotropism. Both forms show thermal SCO with values of 390 K () and 270 K (). An analysis of the crystal structures of and the corresponding Zn(II) () and Co(II) () complexes that are isotypic with reveals that form consists of dimers coupled by strong intramolecular π···π interactions, which is not the case for . In agreement with these findings, investigations of thin films of , where significant π···π interactions should be absent, reveal SCO behavior similar to that of . These results underscore the importance of cooperativity for the spin-transition behavior of this class of complexes.