Synthesis and characterization of four novel mixed (porphyrinato)(phthalocyaninato) sandwich-type europium(III) complexes with [tetrakis(4-chlorophenyl)porphyrinato] and diversely substituted phthalocyaninato ligands

Four novel mixed (porphyrinato)(phthalocyaninato) rare earth double-deckers Eu-III (TClPP)[Pc(t-BuPhO2)(4)] {H2TClPP=tetrakis (4-chlorophenyl)porphyrin, H-2[Pc(t-BuPhO2)(4)]=1,3,10,12(11,13),19,21(20,22),28,30(29,31)-octa-tert-butyl-tetrakis[1,4]benzodioxino [2, 3-b:2',3'-k:2 '',3 ''-t:2 ''',3 '''-e(1)]phthalocyanine}, HEuIII(TClPP)[Pc(alpha-OC4H9)(8)] {H-2[Pc(alpha-OC4H9)(8)]=1,4,8,11,15,18,22,25-octa-butoxyphthalocyanine}, Eu-III (TClPP)[Pc(MeOPhO)(8)]{H-2[Pc(MeOPhO)(8)]=2,3,9,10,16,17,23,24-octakis(4-methoxyphenoxy)phthalocyanine} and Eu-III(TClPP)(Pc(PhS)(8)] {H-2[Pc(PhS)(8)]=2,3,9,10,16,17,23,24-octakis(benzenesulfenyl)phthalocyanine} have been prepared for the first time by treating Eu(acac)(TClPP) with corresponding metal-free phthalocyanine in refluxing 1,2,4-trichlorobenzene (TCB). Typical IR marker bands of the monoanion radical Pc(t-BuPhO2)(4)(center dot-), Pc(MeOPhO)(8)(center dot-) and Pc(PhS)(8)(center dot-) show strong bands at 1310, 1319, and 1318 cm(-1), and are attributed to pyrrole C=C stretchings. The TClPP center dot- IR marker band at ca. 1270-1300 cm(-1) was not observed for these compounds. These facts indicate that the hole in these double-deckers is mainly localized at the phthalocyanine ring. The marker IR band for phthalocyanine monoanionradical, Pc(alpha-OC4H9)(8)(center dot-), appearing at ca. 1312 cm(-1) as a medium absorption band was not observed for HEuIII(TClPP)[Pc(alpha-OC4H9)(8)]. Instead, a significant peak appearing at ca. 1321 cm(-1) with weak intensity is assigned to the pyrrole stretching of the phthalocyanine dianion, Pc(alpha-OC4H9)(8)(2-). This suggests that both the phthalocyanine and porphyrin rings exist as dianions in mixed (porphyrinato)(phthalocyaninato) complex, HEuIII (TClPP2-) [Pc(alpha-OC4H9)(8)(2-)]. The four complexes were characterized by MS, EA, U-V-Vis and IR spectra. (C) 2007 Elsevier B.V. All rights reserved.