Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands

摘要: A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies characterized elemental analysis a range spectroscopic methods. The molecular structures two heteroleptic \[(na)phthalocyaninato](porphyrinato) also determined X-ray diffraction which exhibit slightly distorted square antiprismatic geometry domed ligands. Having very different electronic properties, these compounds systematically investigated for the effects on valence center. On basis (UV−vis, near-IR, IR, Raman), electrochemical, structural data compared those other rare earth(III) counterparts reported earlier, it has found that center adopts an intermediate in complexes. It assumes virtually trivalent state bis(tetra-tert-butylnaphthalocyaninate) as result electron rich naphthalocyaninato ligands, facilitate delocalization from to metal For rest double-deckers, is predominantly tetravalent. valences (3.59−3.68) quantified according their LIII-edge absorption near-edge structure (XANES) profiles.