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

✍ Scribed by Rongming Wang; Renjie Li; Yong Li; Xianxi Zhang; Peihua Zhu; Pui-Chi Lo; Dennis K. P. Ng; Na Pan; Changqin Ma; Nagao Kobayashi; Jianzhuang Jiang

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 219 KB
• Volume: 12
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/chem.200500733

✦ Synopsis

Abstract

The half‐sandwich rare‐earth complexes [M^III^(acac)(TClPP)] (M=Sm, Eu, Y; TClPP=meso‐tetrakis(4‐chlorophenyl)porphyrinate; acac=acetylacetonate), generated in situ from [M(acac)~3~]⋅n H~2~O and H~2~(TClPP), were treated with 1,8,15,22‐tetrakis(3‐pentyloxy)phthalocyanine [H~2~{Pc(α‐OC~5~H~11~)~4~}] (Pc=phthalocyaninate) under reflux in n‐octanol to yield both the neutral nonprotonated and protonated (phthalocyaninato)(porphyrinato) rare‐earth double‐decker complexes, [M^III^{Pc(α‐OC~5~H~11~)~4~}(TClPP)] (1–3) and [M^III^H{Pc(α‐OC~5~H~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~2~Pc(α‐OC~4~H~9~)~8~] gave only the protonated double‐decker complex [Y^III^H{Pc(α‐OC~4~H~9~)~8~}(TClPP)] (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, α‐alkoxylation 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.