期刊
INORGANIC CHEMISTRY
卷 59, 期 12, 页码 7966-7979出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.9b03354
关键词
-
资金
- Deutsche Forschungsgemeinschaft (DFG) [CRC 677]
Two polymorphic modifications (1-I and 1-II) of the new spin crossover (SCO) complex [Fe{H2B(pz)(pypz)}(2)] (pz = pyrazole, pypz = pyridylpyrazole; 1) were prepared and investigated by differential scanning calorimetry (DSC), magnetic measurements, Mossbauer, vibrational, and absorption spectroscopy as well as single-crystal and X-ray powder diffraction. DSC measurements reveal that upon heating the thermodynamically metastable form 1-II to similar to 178 degrees C it transforms into 1-I in an exothermic reaction, which proves that these modifications are related by monotropism. Both forms show thermal SCO with T-1/2 values of 390 K (1-II) and 270 K (1-I). An analysis of the crystal structures of 1-II and the corresponding Zn(II) (2) and Co(II) (3) complexes that are isotypic with 1-I reveals that form II consists of dimers coupled by strong intramolecular pi center dot center dot center dot pi interactions, which is not the case for 1-I. In agreement with these findings, investigations of thin films of I, where significant pi center dot center dot center dot pi interactions should be absent, reveal SCO behavior similar to that of 1-I. These results underscore the importance of cooperativity for the spin-transition behavior of this class of complexes.
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