Synthesis, Properties of Gadolinium Double-Decker Sandwich-Type Complex Containing Tetrabenzoporphyrin Ligand

Abstract

A novel gadolinium double-decker sandwich-type complex with tetrabenzoporphyrin (TBP) ligands-Gd(TBP)2 was synthesized by the reaction of porphyrin 1 with Gd(acac)3. nH2O in boiling 1, 2, 4-Tcb for 15~17 h under Ar. Its structure is characterized byUv-Vis-NIR and HR-MS. The spectroscopic properties show that the longest-wavelength visible band (600-800 nm) and the strong near-IR absorption band centered near 1340 nm of Gd (TBP)2 complex are obviously red-shifted due to the extension of the π conjugated systems derived from the linear benzoannulation in the TBP ring. The magnetic studies also indicate that the observed value of χMT of Gd(TBP)2 complex is close to the combined value of Gd(III) and porphyrin radical anion at room temperature, and antiferromagnetic interaction that possibly results from the intramolecular spin exchange between the porphyrin π-radical electron, and the gadolinium f unpaired electrons dominates its magnetic properties over the whole temperature range. Since the first report of bis(porphyrinato) metal complexes M(Por)2 such as a cerium(IV) bisporphyrinate, Ce(TPP)2 and hydrogen praseodymium(III), PrH(TPP)2 in 1983[1], sandwich-type rare earth complexes with porphyrin ligands have received increasing attentions due to the unusual physical, spectroscopic, redox, electron transfer, and/or conductivity properties resulting from their strong π-π interactions[2-4]. Whereas the chemistry and properties of homoleptic sandwich complexes containing the same pophyrinato ligands of various lanthanide, actinides and group 4 transition metals have been extensively studied[5-6], actually all of them are confined to the sandwich-type complexes containing meso-substituted porphyrin ligands except for octaethylporphyrin (OEP) or octamethylporphyrin (OMP). Little is known about sandwich-like complexes with aromatic ring-fused porphyrin ligands that contain a more delocalized π system. In this paper, we will describe the preparation of a novel gadolinium homoleptic double-decker sandwich-type complex with tetrabenzoporphyrin (TBP) ligand (see Fig.1) as well as their spectroscopic characterization and magnetic studies.

Achievements in the Field of Chemistry of Macroheterocyclic Compounds at the Department of Technology of Fine Organic Synthesis

“…Синтез гомолигандного бис-тетрабензопорфирината гадолиния был осуществлен впервые в 2012 г [37] и требовал использования дорогостоящих реагентов, большой продолжительности, более 120 ч, при этом выход целевого продукта в расчете на исходное соединение составлял ~ 15%. Нами был предложен более удобный метод темплатного синтеза бис-тетрабензопорфиринатов гадолиния, эрбия и лютеция [38].…”