Novel one-pot regioselective route towards heteroleptic lanthanide (phthalocyaninato)(porphyrinato) triple-decker complexes

A novel one-pot method for the regioselective preparation of early heteroleptic lanthanide (porphyrinato)(phthalocyaninato) complexes of double- and triple-decker structure [(Por)Ln(Pc) and (Por)Ln(Pc)Ln(Por), respectively] is developed. Sandwich-type complexes are synthesized for La, Ce and Pr following this procedure, with yields up to 30%. Tetrakis(15-crown-5)-phthalocyanine [(15C5)(4)PcH2] and tetrakis-meso-(4-methoxyphenyl)-porphyrin (An(4)PH(2)) are used as macrocyclic tetrapyrrolic ligands. The complexes are widely characterized with various physico-chemical methods (NMR and UV-vis spectroscopy, MALDI-TOF mass spectrometry). Quantum chemistry calculations for intermediates of the process are performed. The results of calculations explain the high regioselectivity of the triple-decker complex formation in the developed method.