Abstract: | Three series of lanthanide coordination polymers, namely catena‐poly[[lanthanide(III)‐μ2‐(benzene‐1,2‐dicarboxylato)‐μ2‐[2‐(2,2′:6′,2′′‐terpyridin‐4′‐yl)benzoato]] monohydrate], {[Ln(C8H4O4)(C22H14N3O2)]·H2O}n or {[Ln(1,2‐bdc)(L)]·H2O}n, with lanthanide (Ln) = dysprosium (Dy, 1 ), holmium (Ho, 2 ) and erbium (Er, 3 ), poly[bis(μ2‐benzene‐1,3‐dicarboxylato)bis[μ2‐2‐(2,2′:6′,2′′‐terpyridin‐4′‐yl)benzoato]dilanthanide(III)], [Ln2(C8H4O4)2(C22H14N3O2)2]n or [Ln2(1,3‐bdc)2(L)2]n, with Ln = gadolinium (Gd, 4 ), Ho ( 5 ) and Er ( 6 ), and poly[(μ2‐benzene‐1,4‐dicarboxylato)[μ2‐2‐(2,2′:6′,2′′‐terpyridin‐4′‐yl)benzoato]lanthanide(III)], [Ln(C8H4O4)(C22H14N3O2)]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 Ln2(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 Ln2(COO)2 units. Compounds 7 – 10 display 8‐connected 3D frameworks with the topological type rob , consisting of Ln2(COO)2 units. The influence of the coordination orientations of the aromatic dicarboxylate groups on the crystal structures is discussed. |