Synthesis, Characterization, Nonlinear Absorption and Electrochromic Properties of Double‐Decker Octakis(mercaptopropylisobutyl‐POSS)phthalocyaninatolanthanide(III) Complexes

In this study, the sandwich‐like bis(phthalocyaninato)lanthanide(III) complexes MPc 2 (M = Lu, Gd) have been prepared. The reaction of 4,5‐bis(mercaptopropylisobutyl‐POSS)phthalonitrile ( 1 ) [POSS: polyhedral oligomeric silsesquioxane] with lithium gave the dilithium octakis(mercaptopropylisobutyl‐POSS)phthalocyaninate which was further reacted in situ with Lu(OAc) 3 · 3H 2 O and Gd(OAc) 3 · 4H 2 O in 1‐pentanol to give compounds 2 and 3 , respectively. The structure of the target compounds was confirmed by elemental analysis, UV/Vis and IR spectroscopic as well as MALDI‐TOF mass spectrometric techniques. The nonlinear absorption andoptical limiting (OL) performance of 2 and 3 are investigated by means of the Z‐scan technique. While 2 exhibits a good nonlinear absorption, 3 possesses a low nonlinear absorption. The ratio of the excited‐state to ground‐state absorption cross sections, κ , the effective nonlinear absorption coefficient, β eff , and the energy density, F sat , were determined for 2 . The results indicated that 2 possesses a good combination of optical limiting parameters.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)