Crystal engineering of new functional coordination polymers of Lanthanide-Multicarboxylates

Abstract

Designs and syntheses of new series of lanthanide coordination polymers (LnCPs) using mixed phthalate (phth2-) and one of the following dicarboxylates, i.e. terephthalate (bdc2-; Chapter 3), adipate (ad2-; Chapter 4), azobenzene-4,4ʹ-dicarboxylate (abdc2-; Chapter 5) and (ΔLLL)2-[Co3(ʟ-cys)6] 3- metalloligand (Chapter 6), are reported as summarized in Scheme 1. The effects of the mixed ligands on the fabricated framework structures and their photoluminescence as well as thermogravimetric property, and satervapor adsorption/desorption are presented and discussed. The use of two rigid and good sensitizing phth2-and bdc2-is reported in Chapter 3. The combination of the two ligands led to three-dimensional [Ln(bdc)0.5(phth)(H2O)2], where LnIII = EuIII (VIa), GdIII (VIIa), TbIII (VIIIa), HoIII (Xa), ErIII (XIa) and TmIII (XIIa). The phth2-linker links the discrete {LnIIIO8} units into the two-dimensional [Ln(phth)(H2O)2] sheets, which are then pillared by bdc2-leading to the three-dimensional framework. The presence of the two good sensitizing phth2-and bdc2-evidently changed the temperature-dependent photoluminescent behaviors of the monometallic VIa and VIIIa from those of [Ln2(phth)3(H2O)] (LnIII = EuIII and TbIII). Rendered by the TbIII -toEuIII energy transfer, the bimetallic [EuxTb1-x(bdc)0.5(phth)(H2O)2] (XVa-XVIIa) exhibited sensitive temperature-dependent photoluminescent behaviors in physiological and high temperature ranges.