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用XPS测定了5种含Fc~Ⅲ杂多阴离子中Fe_(2■)和O_(1■)的结合能及Fe_(2■3/2)的伴峰强度。结合磁化率和差减红外光谱,研究了杂多阴离子中铁的自旋态。证实二聚体(SiFeW_(11))_2O中含有Fe—O—Fed-pπ键,相邻铁原子上的d电子发生了反磁性交换。讨论了骨架原子及中心原子对杂多阴离子中铁的电子云密度的影响。
The binding energies of Fe_ (2 ) and O_ (1 ◦) and the peak intensities of Fe_2 (2 3/2) in five kinds of Fc ~ Ⅲ heteropolyanions were determined by XPS. Combined with susceptibility and difference subtraction infrared spectroscopy, the spin states of iron in heteropolyanions were studied. It is confirmed that the dimer (SiFeW_ (11)) _2O contains Fe-O-Fed-pπ bonds and the d electrons on adjacent iron atoms are diamagnetic exchanged. The effects of framework atoms and central atoms on the electron cloud density of iron in heteropolyanions are discussed.