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 EuIII(TClPP)[Pc(t -BuPhO2)4] {H2TClPP = tetrakis(4-chlorophenyl)porphyrin, H2[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(α-OC4H9)8] {H2[Pc(α-OC4H9)8] = 1,4,8,11,15,18,22,25-octa-butoxy-phthalocyanine}, EuIII(TClPP)[Pc(MeOPhO)8]{H2[Pc(MeOPhO)8] = 2,3,9,10,16,17,23,24-octakis(4-methoxyphenoxy)phthalocyanine} and EuIII(TClPP)[Pc(PhS)8] {H2[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 View the MathML sourcePc(t-BuPhO2)4-, View the MathML sourcePc(MeOPhO)8- and View the MathML sourcePc(PhS)8- show strong bands at 1310, 1319, and 1318 cm−1, and are attributed to pyrrole Cdouble bond; length as m-dashC stretchings. The TClPPradical 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, View the MathML sourcePc(α-OC4H9)8-, appearing at ca. 1312 cm−1 as a medium absorption band was not observed for HEuIII(TClPP)[Pc(α-C4H9)8]. Instead, a significant peak appearing at ca. 1321 cm−1 with weak intensity is assigned to the pyrrole stretching of the phthalocyanine dianion, View the MathML sourcePc(α-OC4H9)82-. This suggests that both the phthalocyanine and porphyrin rings exist as dianions in mixed (porphyrinato)(phthalocyaninato) complex, View the MathML sourceHEuIII(TClPP2-)[Pc(α-OC4H9)82-]. The four complexes were characterized by MS, EA, UV–Vis and IR spectra.