Structural investigation of one‐ and three‐dimensional lanthanide(III) coordination polymers based on functionalized terpyridine carboxylate and aromatic dicarboxylate ligands

摘要

Three series of lanthanide coordination polymers, namely catena ‐poly[[lanthanide(III)‐μ 2 ‐(benzene‐1,2‐dicarboxylato)‐μ 2 ‐[2‐(2,2′:6′,2′′‐terpyridin‐4′‐yl)benzoato]] monohydrate], {[Ln(C 8 H 4 O 4 )(C 22 H 14 N 3 O 2 )]·H 2 O} n or {[Ln(1,2‐bdc)( L )]·H 2 O} n , with lanthanide (Ln) = dysprosium (Dy, 1 ), holmium (Ho, 2 ) and erbium (Er, 3 ), poly[bis(μ 2 ‐benzene‐1,3‐dicarboxylato)bis[μ 2 ‐2‐(2,2′:6′,2′′‐terpyridin‐4′‐yl)benzoato]dilanthanide(III)], [Ln 2 (C 8 H 4 O 4 ) 2 (C 22 H 14 N 3 O 2 ) 2 ] n or [Ln 2 (1,3‐bdc) 2 ( L ) 2 ] n , with Ln = gadolinium (Gd, 4 ), Ho ( 5 ) and Er ( 6 ), and poly[(μ 2 ‐benzene‐1,4‐dicarboxylato)[μ 2 ‐2‐(2,2′:6′,2′′‐terpyridin‐4′‐yl)benzoato]lanthanide(III)], [Ln(C 8 H 4 O 4 )(C 22 H 14 N 3 O 2 )] n or [Ln(1,4‐bdc)( L )] n , with Ln = Dy ( 7 ), Ho ( 8 ), Er ( 9 ) and ytterbium (Yb, 10 ), were synthesized under hydrothermal conditions and characterized by elemental analysis, IR and single‐crystal X‐ray diffraction. Compounds 1 – 3 possess one‐dimensional loop chains with Ln 2 (COO) 2 units, which are extended into three‐dimensional (3D) supramolecular structures by π–π interactions. Isostructural compounds 5 and 6 show 6‐connected 3D networks, with pcu topology consisting of Ln 2 (COO) 2 units. Compounds 7 – 10 display 8‐connected 3D frameworks with the topological type rob , consisting of Ln 2 (COO) 2 units. The influence of the coordination orientations of the aromatic dicarboxylate groups on the crystal structures is discussed.