Four distinctive 1-D lanthanide carboxylate coordination polymers: Synthesis, crystal structures and spectral properties

Four novel lanthanide coordination polymers [Pr(mal)(OH)(bipy) · 2H2O]n (1), {[Dy1(SBA)3(H2O)2][Dy2(SBA)3(H2O)2] · 4H2O}n (2), {[Tb(OHnic)(Onic)(H2O)5 · (OHnicH)] · H2O}n (3) and {[Sm(OHnic)(Onic)(H2O)5 · (OHnicH)] · H2O}n (4) (Hmal = maleic acid, HSBA = 4-sulfobenzoic acid, OHnicH = 6-hydroxynicotinic acid and bipy = 2,2′-bipyridine) have been synthesized and determined by single crystal X-ray diffraction. Complex 1 is a 1-D helical chain with seven-coordinated praseodymium centers. Complex 2 forms 1-D chain-like molecular structure containing two crystallographically unique dysprosium centers, the Dy1 center is seven-coordinated while Dy2 is eight-coordinated. The isomorphous complexes 3 and 4 exhibit an unprecedented 1-D chain-like polymeric structure through hydroxyl oxygen atoms of bridging Onic2− anions linking up the neighboring central ions, and there exist three types of 6-OHnicH ligands in the structural unit which is rare for lanthanide carboxylate complexes. The photophysical properties of these complexes were studied using ultraviolet absorption spectra, fluorescence excitation and emission spectra.

Four new lanthanide carboxylate complexes have been synthesized. Single crystal X-ray diffraction analyses reveal that all the complexes form 1-D molecular structures. Especially, complexes 1 and 2 have seven-coordinated centers; in the structures of the isomorphous complexes 3 and 4, there exist three types of 6-OHnicH ligands: a bridging Onic2− anion, a chelating HOnic− anion and a neutral H2Onic molecule.Figure optionsDownload as PowerPoint slide