A 3 B‐Type Phthalocyanine‐Based Homoleptic Lanthanide(III) Double‐Decker π‐Radical Complexes Bearing Functional Hydroxy Groups: Synthetic Approach, Spectral Properties and Electrochemical Study

The sandwich lanthanide(III) complexes BnO,Bu Pc 2 Ln ( 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 ] · n H 2 O and BnO,Bu PcH 2 by heating these compounds in n ‐hexadecanol, and then treating the reaction solution with H 2 SO 4 to yield the corresponding neutral double‐decker complexes HO,Bu Pc 2 Ln ( 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.