화학공학소재연구정보센터
Inorganic Chemistry, Vol.58, No.1, 506-515, 2019
Lanthanoid Heteroleptic Complexes with Cucurbit[5]uril and Dicarboxylate Ligands: From Discrete Structures to One-Dimensional and Two-Dimensional Polymers
Lanthanoid heteroleptic complexes with cucurbit[5]uril {Q[5]} and two dicarboxylate ligands, e.g., diglycolic acid (H(2)DGC) and glutaric acid (H(2)GT), have been investigated with six new compounds featuring a tetrametallic and dimetallic discrete structures, a one-dimensional (1D) polymer, and three two-dimensional (2D) polymers with a unique honeycomb-type topology being synthesized and structurally characterized. [La-4(Q[5])(3)(DGC)(2)(NO3)(2)(H2O)(12)][La(DGC)-(H2O)(6)]center dot 7NO(3)center dot nH(2)O (1) has a tetrametallic structure constructed with three bis-bidentate Q[5] ligands linking two [La(DGC)(H2O)(2)](+) species in the middle and two [La(H2O)(4)(NO3)](2+) species at both ends. [Ce-2(Q[5])(DGC)(NO3)-(H2O)(10)]center dot 3NO(3)center dot 4H(2)O (2) has a dimetallic structure built up with a bis-bidentate Q[5] ligand linking [Ce(DGC)-(H2O)(3)(NO3)] and [Ce(H2O)(7)](3+) on each side of the Q[5] portals. [Ce-3(Q[5])(3)(DGC)(2)(H2O)(9)][Ce(DGC)(H2O)(6)](2)center dot 7NO(3)center dot nH(2)O (3) has a 1D polymeric structure built up with bis-bidentate Q[5] ligands in-turn linking one [Ce(H2O)(6)](3+) and two [Ce(DGC)(H2O)(6)](1+) cationic species. [Ln(2)(Q[5])(2)(GT)(H2O)(6)]center dot 4NO(3)center dot nH(2)O [Ln = La (4), Ce (5) and Nd (6)] have similar 2D polymeric structures built up with two types of 9-fold coordinated Ln polyhedra linked by Q[5] via bis-bidentate carbonyl groups on both sides forming 1D chains which are further connected by bridging GT(2-) ligands to form 2D polymers with a unique honeycomb-type topology. Their vibrational modes and electronic structures have also been investigated.