A Series of New Three-Dimensional d–f Heterometallic Coordination Polymers with Rare 10-ConnectedbctNet Topology Based on Planar Hexanuclear Heterometallic Second Building Units

Abstract

A series of new three-dimensional (3D) d−f heterometallic coordination polymers, namely, [LnM(μ 5 -PyIDC)(μ 2 -INIC)(μ 3 -INIC)]•x-H 2 O [Ln = Sm, M = Co, x = 3 (1); Ln = Sm, M = Ni, x = 1 (2); Ln = Eu, M = Co, x = 3 (3); Ln = Eu, M = Cd, x = 3 (4); Ln = Eu, M = Zn, x = 3 (5); Ln = Gd, M = Co, x = 3 (6); Ln = Gd, M = Cd, x = 3 (7); Ln = Tb, M = Co, x = 3 (8); Ln = Tb, M = Cd, x = 2 (9); Ln = Tb, M = Zn, x = 3 (10); H 3 PyIDC = 2-(pyridine-3-yl)-1H-4,5-imidazoledicarboxylic acid; HINIC = isonicotinic acid], have been successfully synthesized under hydrothermal conditions and structurally characterized. All the complexes are isostructural and exhibit novel 3D pillar-layered coordination frameworks constructed by the linkages of 2D heterometallic layers and INIC − pillars. Topological analysis indicates that those complexes possess a rare uninodal 10-connected bct topology based on planar hexanuclear heterometallic [Ln 2 M 4 (PyIDC) 2 ] second building units. To the best of our knowledge, complexes 1−10 represent examples of 3D lanthanide−transition heterometal−organic coordination polymers with highly connected bct networks. Moreover, the luminescence properties of complexes 3−5 and 7−10 and the magnetic properties of 6−8 were also investigated.

Syntheses, Structures, and Photoluminescence Properties of a Series of 3D Zn‐Ln Heterometallic Complexes with 2,3‐Pyrazine Dicarboxylic Acid as a Bridging Ligand

“…It can be seen that the correlation emission band of the ligand is in the range of 390–550 nm, and the strongest emission peak is at 423 nm. The weak broad bands from 390 to 550 nm may be due to ligand–metal charge transfer (LMCT) from the Pzdc 2– ligand to the Zn 2+ ion , . The characteristic emission peaks of the Sm III ion indicate that energy can be efficiently transferred from the Pzdc 2– ligand to the Sm 3+ ion.…”

Syntheses, structures, and luminescence of two Zn(II) coordination polymers based on 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole and carboxylates

“…Yield 15% (based on the Zn). Elemental analysis Calculated (%) for C 24 (2). A mixture of HIPT (10.6 mg, 0.05 mmol), Zn(OAc) 2 ·2H 2 O (10.9 mg, 0.05 mmol), 2-propyl-1 h-imidazole-4,5-dicarboxyacid (H 3 PrIDC, 9.9 mg, 0.05 mmol), and distilled water (6 mL) was sealed in a 10-mL Teflon-lined stainless steel autoclave, and HCl (1 M/L) was used to adjust the pH at 3-6.…”

“…Only a few CPs based on HIPT were reported [15][16][17][18][19][20][21][22]. Incorporation of more types of metal ions or organic ligands into a single unique framework is worth studying because the functionality of CPs is mainly derived from metal ions and ligands [23,24]. The combination of nitrogen donor ligands and aromatic carboxylate has been proven to be an effective strategy for constructing diverse mixed-ligand CPs [25,26].…”

Construction of Four Coordination Polymers based on 2-[4-(Pyridine-4-yl)phenyl]-1H -imidazole-4,5-dicarboxylic Acid

“…Encouraged by these productive findings, many research groups have focused on the coordination features of various functionalized H 3 IDC ligands in recent years. Indeed, H 3 IDC derivatives with diverse substituent groups at the 2‐position of the imidazole ring, including nonaromatic groups and aromatic groups, have been widely used as effective building blocks for the construction of new CPs.…”

“…Our group, among others, has recently designed and synthesized several analogue ligands of H 3 IDC, such as 2‐hydroxymethyl‐1 H ‐imidazole‐4,5‐dicarboxylic acid (H 4 hmIDC), 2‐trifluoromethyl‐1 H ‐4,5‐imidazole dicarboxylic acid (H 3 TFMIDC),, 2‐pyridyl‐4,5‐imidazole‐dicarboxylic acid (H 3 PyIDC), and so on, to build up diverse CPs. It has been found that the introduced substituent groups not only may induce spatial effects on the adjacent carboxylate groups, but also can provide additional coordination sites, leading to the construction of a series of new CPs.…”