Two Series of Substituent‐Group‐Directed Adipate‐Based Lanthanide Coordination Polymers: Syntheses, Structures, Photoluminescence, and Magnetism

Abstract

Two series of lanthanide‐organic coordination polymers (CPs) [Ln2(L1)3(H2O)4] [Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), and Dy (6), H2L1 = 3‐methyl‐adipic acid] and [Ln4(L2)6(H2O)4] [Ln = Nd (7), Sm (8), Eu (9), Gd (10), Tb (11), and Dy (12), H2L2 = 3‐tert‐butyl‐adipic acid] have been synthesized by the solvothermal reactions of lanthanide salts with two types of flexible substituent adipates. All of these CPs were characterized by single‐crystal X‐ray diffraction, elemental analysis, IR spectroscopy, powder X‐ray diffraction, and thermal analysis. Structural analyses reveal that CPs 1–6 and 7–12 are isostructural, respectively. CPs 1–6 show a two‐dimensional (2D) layer constructed from the 3‐methyl‐adipate anions bridging two types of binuclear Ln2 units. The adjacent 2D layers are further extended into a three‐dimensional (3D) supramolecular framework through the hydrogen‐bonding interactions. CPs 7–12 also exhibit a 2D structure. The carboxyl groups of 3‐tert‐butyl‐adipate link four types of TbIII ions to form a one‐dimensional (1D) inorganic TbIII chain. The neighboring 1D inorganic TbIII chains are further connected by the 3‐tert‐butyl‐adipate anions to construct a 2D network. The effect of substituent groups on the formation of adipate‐based lanthanide CPs as well as the photoluminescence and magnetic properties of 1–12 were investigated in detail.

Terbium(iii)-based coordination polymer with millimeter-size single crystals and high selectivity and sensitivity for folic acid

“…Coordination polymers (CPs) composed of organic ligands and metal ions have attracted more and more attention because of their novel structures and their potential applications in gas adsorption and separation, luminescence sensors, magnetism, and catalysis in recent years. [14][15][16][17][18] In particular, lanthanide coordination polymers (Ln-CPs) which have excellent optical properties, such as a narrow emission band, high color purity and a long fluorescence lifetime, 19,20 have been widely used in the detection of heavy metal ions, anions, biomolecules and solvent molecules due to their novel topological structure, as well as great possibilities of structural modification and functionalization. [21][22][23][24] The design and selection of suitable organic ligands and central metal ions are prerequisites for a diversity of complex structures and functions.…”

On the Importance of H-Bonding Interactions in the Enclathration of Boric Acids in Na(I) Polymers: Experimental and Theoretical Studies

“…Saturated dicarboxylic acids also serve as suitable H-bonding acceptors [29,30], resulting in the development of bridging metal-organic compounds with various desired self-assembled architectures [31,32]. As a consequence, adipic acid has evolved as a potential bridging ligand to form interesting coordination polymers with potential applications [33][34][35]. The dicarboxylate groups of fumarate anion (an unsaturated dicarboxylate) also have the ability to coordinate with the metal centers in multidentate fashion [36].…”

Microwave-assisted synthesis of anhydrous lanthanide-based coordination polymers built upon benzene-1,2,4,5-tetracarboxylic acid

“…Lanthanide coordination polymers is a fascinating class of materials which is widely investigated due to their potential applications in gas storage [1][2][3][4][5][6] , catalysis 7 , magnetism [8][9][10][11][12] or luminescence [13][14][15][16][17] . Most of them are built with benzoic multicarboxylate ligands which are versatile building blocks to obtain various coordination polymers due to their variety of bridging abilities 2,[18][19][20] .…”