Controlling the Nature of Mixed (Phthalocyaninato)(porphyrinato) Rare-Earth(III) Double-Decker Complexes:The Effects of Nonperipheral Alkoxy Substitution of the Phthalocyanine Ligand

摘要

The half-sandwich rare-earth complexes [M~(III)(acac)(TClPP)] (M =Sm,Eu,Y;TClPP=meso-tetrakis(4-chlorophenyl)porphyrinate;acac=ace-tylacetonate),generated in situ from [M(acac)_3] centre dot nH_2O and H_2(TClPP),were treated with 1,8,15,22-tetrakis(3-pentyl-oxy)phthalocyanine [H_2(Pc(a-OC_5H_(11))_4)] (Pc=phthalocyaninate) under reflux in n-octanol to yield both the neutral nonprotonated and proton-ated (phthalocyaninato)(porphyrinato) rare-earth double-decker complexes,[M~(III)(Pc(alpha-OC_5H_(11))_4)(TClPP)] (1-3) and [M~(III)H(Pc(alpha-OC_5H_(11))_4)(TClPP)] (4-6),respectively.In contrast,reaction of [Y~(III)(acac)(TClPP)] with 1,4,8,11,15,18,22,25-octakis(1-butyloxy)-phthalocyanine [H_2Pc(alpha-OC_4H_9)_8] gave only the protonated double-decker complex [Y~(III)H{Pc(alpha-OC_4H_9)_8}-(TC1PP)] (7).These observations clearly show the importance of the number and positions of substituents on the phthalocyanine ligand in controlling the nature of the (phthalocyaninato)-(porphyrinato) rare-earth double-deckers obtained.In particular,alpha-alkoxyla-tion of the phthalocyanine ligand is found to stabilize the protonated form,a fact supported by molecular-orbital calculations.A combination of mass spectrometry,NMR,UV-visible,near-IR,MCD,and IR spectroscopy,and X-ray diffraction analyses,facilitated the differentiation of the newly prepared neutral nonprotonated and protonated double-decker complexes.The crystal structure of the protonated form has been determined for the first time.