Three-Dimensional Extended Frameworks Constructed from Dinuclear Lanthanide(III) 1,4-Naphthalenedicarboxylate Units with Bis(2,2′-biimidazole) Templates: Syntheses, Structures, and Magnetic and Luminescent Properties

Eight unprecedented Ln-NDC coordination polymers with BBI as templates {[HBBI][Ln(NDC) 2 (H 2 O)]·H 2 O [Ln = La ( 1 ), Pr ( 2 )], [HBBI] 2 [Sm(NDC) 2 (H 2 O)] 2 ·1/2H 2 O ( 3 ), and [HBBI][Ln(NDC) 2 (H 2 O)] [Ln = Eu ( 4 ), Gd ( 5 ), Tb ( 6 ), Dy ( 7 ), Er ( 8 )] [Ln = lanthanide, H 2 NDC = 1,4-naphthalenedicarboxylic acid, BBI = bis(2,2′-biimidazole)]} have been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectra, and single-crystal X-ray diffraction. Complexes 1 – 8 crystallize in the monoclinic space group P 2 1 / c and display similar (8,8)-connected 3-D frameworks with different dinuclear Ln secondary building units due to the effect of Ln contraction and diverse coordination modes of NDC 2– ligands. As the ionic radii of Ln ions decrease, the coordination numbers of Ln ions decrease from 10, to 9, to 8. The variable-temperature magnetic properties of 2 – 8 have been investigated. The strong fluorescent emissions of 4 demonstrate that ligand-to-Eu III energy transfer is efficient. In addition, thermogravimetric analyses and optical diffuse reflectance spectra of these compounds are also described.