Abstract
Heteroleptic porphyrinato/phthalocyaninato rare earth(III) triple-decker compounds M 2( Por )2( Pc ') (1a-4a) and M 2( Por )( Pc ')2 (1c-4c) ( M = Eu , Tb ; Por = TDOPP , Pc ' = OOPc or Por = TpClPP , Pc ' = Pc where H 2(TDOPP) = 5,10,15,20-tetrakis(4-n-dodecyloxyphenyl)porphyrin, H2[OOPc] = 2,3,9,10,16,17,23,24-octakis(n-octyloxy)phthalocyanine, H 2(TpClPP) = 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin, H 2( Pc ') = general phthalocyanine, and H 2( Pc ) = unsubstituted phthalocyanine) were obtained by the cyclic tetramerization of the corresponding dicyanobenzenes 7 using monoporphyrinato rare earth(III) acetylacetonates M(Por)acac as templates with catalysis by the organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Double-decker complexes M(Por)(Pc') ( M = Eu , Tb ; Por = TDOPP , Pc ' = OOPc or Por = TpClPP , Pc ' = Pc ) (1b-4b) were isolated as side products. For the purpose of comparative study, homo- and hetero-dinuclear rare earth triple-deckers with one porphyrinato and two phthalocyaninato ligands M2(Por)( Pc ')2 (1c, 2c) ( M = Eu , Tb ; Por = TDOPP , Pc ' = OOPc ) and ( Por ) M ( Pc ') M '( Pc ')( M ≠ M ' = Eu , Tb ) (5c, 6c) were also prepared using the raise-by-one-story method. The complexes were characterized by UV-vis, near-IR, IR and mass spectra. The comparison between 1 H NMR spectra of the two series of triple-decker compounds a and c, and also between the substituted phthalocyanine- and unsubstituted phthalocyanine-containing europium triple-deckers, renders it possible to assign the aromatic proton signals unambiguously.
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