Cation-Induced Supramolecular Organization of Double- and Triple-Decker Rare-Earth Complexes with Tetra(15-crown-5) -Substituted Phthalocyanine as Probed by Electronic Absorption Spectroscopy

摘要

The cation-induced supramolecular organization of sandwich crown-substituted rare-earth phthalocyaninates in organic solvents in the presence of alkali-metal thiocyanates has been studied by spectrophotometry. KSCN reacts with a triple-decker lutetium complex in CHCl_3 to form the cofacial dimers 2Lu_2(R_4Pe)_3 4KSCN (R_4Pc~(2-) = 4,5,4',5',4",5",4"',5"'-tetrakis(1,4,7,10,13-pentaoxatridecamethylene)phthalocyaninate ion). The nitrogenous base l,8-diazabicyclo[5.4.0]undec-7-ene can reduce monoradical rare-earth phthalocyaninate (Y~(3+), Gd~(3+), Yb~(3+), Lu~(3+)). The interaction of alkali-metal (K~+, Rb~+, Cs~+) thiocyanates with one-electron-reduced diphthalocyaninates forms contributes to their organization in polymeric cofacial aggregates with the composition {[Ln(R_4Pc)_2~- M~+] 3MSCN}_N.