Inorganic Chemistry Laboratory, Department of Chemistry , University of Oxford , South Parks Road , Oxford OX1 3QR , U.K.
Inorg Chem. 2019 Sep 16;58(18):11961-11970. doi: 10.1021/acs.inorgchem.9b00960. Epub 2019 May 28.
With the exception of systems containing Cu, complex metal oxides containing paramagnetic transition-metal cations in square-planar coordination are rare. However, by either introducing chalcogenide, pnictide, or halide anions to form mixed-anion systems or by utilizing low-temperature topochemical reduction via anion deintercalation, an extensive range of phases containing square-planar MO units can be prepared. The crystal chemistry of a series of transition-metal AMOX oxyhalide and AMOBX oxychalcogenide and oxypnictide phases is reviewed along with how their magnetic behavior changes as a function of the transition-metal and electron count. As a contrast, these mixed-anion phases are then compared to a series of topochemically reduced, metastable transition-metal oxides that also contain square-planar-coordinated transition metals, to more fully illustrate the magnetic properties of extended frameworks of square-planar MO units.
除了含有铜的系统之外，在正方形配位的顺磁过渡金属阳离子的复杂金属氧化物很少见。然而，通过引入硫属化物、磷化物或卤化物阴离子形成混合阴离子体系，或者通过利用阴离子脱嵌的低温拓扑化学反应，可以制备出含有正方形配位 MO 单元的广泛的相。本文综述了一系列过渡金属 AMOX 卤氧化物和 AMOBX 氧硫族化物和氧磷化物相的晶体化学，并讨论了它们的磁行为如何随过渡金属和电子数的变化而变化。作为对比，然后将这些混合阴离子相与一系列拓扑化学还原的、亚稳的过渡金属氧化物进行了比较，这些氧化物也含有正方形配位的过渡金属，以更全面地说明正方形配位 MO 单元的扩展框架的磁性。
