A_3type phthalocyanine-based homoleptic lanthanide(III) double-decker π-radical complexes bearing functional hydroxy groups: Synthetic approach, spectral properties and electrochemical study

摘要

The sandwich lanthanide(III) complexes ~(BnO,Bu)Pc_2Ln (~(BnO,Bu)Pc = 2-benzyloxy-9,10,16,17,23,24-hexa-n- butylphthalocyaninate; Ln = Eu, Lu) (1a, 1b) were obtained from [Ln(acac) _3]·nH_2O and ~(BnO,Bu)PcH_2 by heating these compounds in n-hexadecanol, and then treating the reaction solution with H_2SO_4 to yield the corresponding neutral double-decker complexes ~(HO,Bu)Pc_2Ln (~(HO,Bu)Pc = 9,10,16,17,23,24-hexa-n-butyl-2-hydroxyphthalocyaninate) (2a, 2b), which are promising structural building blocks and stable phenolic hydroxy group containing π-radical species. A combination of UV/Vis/NIR, NMR spectroscopy, MALDI-TOF mass spectrometry, cyclic voltammetry and spectroelectrochemistry provided unambiguous characterization of the newly prepared bis(phthalocyanines), and also allowed their stability and behavior in solution to be investigated.