Synthetic, spectroscopic and theoretical study of novel supramolecular structures composed of lanthanide phthalocyanine double-decker complexes

This paper reviews the authors' attempts to create novel supramolecular structures composed of bis(phthalocyaninato)lanthanides and the analysis of their geometric and electronic structures. We synthesized tetra- and mono-crown-substituted bis(phthalocyaninato)lutetium, which show different aggregate forms under various conditions. The aggregate structures fall into three categories: (1) a D-4/i vertically stacked structure formed from the tetra-crown complex and cations such as K+ or NH4+; (2) a sliding form composed of tetra-crown complexes in methanol/chloroform mixed solvent; and (3) a pivoted form constructed from mono-crown substituted complexes with cations such as K+. The electronic structure of the supramolecular structures and magnetic interactions within are discussed. (C) 2002 Elsevier Science B.V. All rights reserved.