Synthesis, spectral properties and supramolecular dimerisation of heteroleptic triple-decker phthalocyaninato complexes with one outer crown-substituted ligand

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• 作者：Alex ; er G. Martynov ; Olga V. Zubareva ; Yulia G. Gorbunova ; Sergey G. Sakharov ; Aslan Yu. Tsivadze
• 关键词：Rare earths ; Macrocyclic ligands ; Phthalocyanines ; Heteroleptic complexes ; Supramolecular dimerisation
• 刊名：Inorganica Chimica Acta
• 出版年：2009
• 出版时间：1 January 2009
• 年：2009
• 卷：362
• 期：1
• 页码：11-18
• 全文大小：320 K

文摘

Four complexes – [(15C5)₄Pc]M(Pc)M(Pc), (Pc²⁻ – phthalocyaninato-dianion, [(15C5)₄Pc]²⁻ – 2,3,9,10,16,17,24,25-tetrakis(15-crown-5)phthalocyaninato-dianion, M = Sm, Dy, Tm, Y) were obtained via the reaction of M(Pc)₂, H₂[(15C5)₄Pc] and M(acac)₃. The influence of the stability of starting M(Pc)₂ on the yields of target compounds was investigated. Increasing the stability of M(Pc)₂ leads to higher yields of [(15C5)₄Pc]M(Pc)M(Pc) and lower yields of scrambling products. All complexes were characterized by ¹H NMR, UV–Vis and FT-IR spectroscopy as well as MALDI TOF mass-spectrometry. The analysis of ¹H NMR spectra was performed in terms of lanthanide-induced shifts. Cation-induced dimerisation was studied by means of spectrophotometric titration. Supramolecular dimers {2[(15C5)₄Pc]M(Pc)M(Pc) · 4K⁺} are the largest discrete cofacial supramolecular assemblies built of phthalocyanine building blocks reported up-to-date. The observed increase of the intermolecular excitonic interaction between building blocks with the increase of REE(III) size is tentatively explained in terms of metal-size dependent deformation of phthalocyanine ligands in sandwich complexes.