ENGINEERING THE DYNAMIC MAGNETIC PROPERTIES IN CYANIDE-BRIDGED COORDINATION CLUSTERS

Abstract

Among the myriad of functional supramolecular assemblies, molecules with dynamic magnetic properties, for example spin crossover (SCO) and charge transfer (CT), have been recognized as promising candidates for the development of next-generation molecular devices. In this thesis, we focused on homometallic FeIII-CN-FeII complexes which may either show the most prevalent SCO behavior according to the HS-LS transition of Fe(II) centers or the metal-to-metal charge transfer (MMCT) between the [FeIII-CN-FeII] and [FeII-CN-FeIII] electronic states. Firstly, we described the rarely observed MMCT behavior in two cubic [FeIII4FeII4] compounds. The solely CT process without spin transition involved is different with those previous reported heterometallic [Fe-CN-Co] system. Secondly, the finely manipulating of transition temperature (T1/2) of SCO was demonstrated in three isostructural [FeIII2FeII2] molecular squares by introducing NCE- co-ligands. Lastly, we discussed an atypical SCO behavior of a [AuI(CN)2]-armed [FeIII2FeII2] square compound in which reverible symmetric-breaking phase transition occures in a synergetic way with SCO.