A new family of lanthanide coordination polymers based on 3,3′‐[(5‐carboxylato‐1,3‐phenylene)bis(oxy)]dibenzoate: synthesis, crystal structures and magnetic and luminescence properties

• Published in: Acta crystallographica. Section C, Crystal structure communications Crystal structure communications, 2020-08, Vol.76 (8), p.763-770
• Main Authors: Yang, Dong-Dong, Lu, Li-Ping, Zhu, Miao-Li
• Format: Article
• Language: English
• Subjects: Ambient temperature; Antiferromagnetism; Aromatic compounds; Atomic radius; Cerium; Chemical analysis; coordination polymer; Coordination polymers; Crystal structure; Dimethylformamide; Europium; Gadolinium; Infrared analysis; Infrared spectroscopy; Interlayers; Ions; lanthanide; Ligands; Luminescence; Magnetic properties; magnetism; Neodymium; Optical materials; Optical properties; polycarboxylic acid; Polymers; Praseodymium; Samarium; Thermogravimetric analysis
• ISSN: 2053-2296; 0108-2701; 2053-2296; 1600-5759
• DOI: 10.1107/S2053229620009547

Six two‐dimensional (2D) coordination polymers (CPs), namely, poly[{μ5‐3,3‐[(5‐carboxylato‐1,3‐phenylene)bis(oxy)]dibenzoato‐κ6O1:O1′:O3,O3′:O5:O5′}bis(N,N‐dimethylformamide‐κO)lanthanide(III)], [Ln(C21H11O8)(C3H7NO)2]n, with lanthanide/Ln = cerium/Ce for CP1, praseodymium/Pr for CP2, neodymium/Nd for CP3, samarium/Sm for CP4, europium/Eu for CP5 and gadolinium/Gd for CP6, have been prepared by solvothermal methods using the ligand 3,3′‐[(5‐carboxy‐1,3‐phenylene)bis(oxy)]dibenzoic acid (H3cpboda) in the presence of Ln(NO3)3. The complexes were characterized by single‐crystal X‐ray and powder diffraction, IR spectroscopy, elemental analysis and thermogravimetric analysis (TGA). All the structures of this family of lanthanide CPs are isomorphous with the triclinic space group P and reveal that they have the same 2D network based on binuclear LnIII units, which are further extended via interlayer C—H…π interactions into a three‐dimensional supramolecular structure. The carboxylate groups of the cpboda3− ligands link adjacent LnIII ions and form binuclear [Ln2(RCOO)4] secondary building units (SBUs), in which each binuclear LnIII SBU contains four carboxylate groups from different cpboda3− ligands. Moreover, with the increase of the rare‐earth Ln atomic radius, the dihedral angles between the aromatic rings gradually increase. Magnetically, CP6 shows weak antiferromagnetic coupling between the GdIII ions. The solid‐state luminescence properties of CP2, CP5 and CP6 were examined at ambient temperature and CP5 exhibits characteristic red emission bands derived from the Eu3+ ion (CIE 0.53, 0.31), with luminescence quantum yields of 22%. Therefore, CP5 should be regarded as a potential optical material. A new family of lanthanide(III) coordination polymers based on 3,3′‐[(5‐carboxy‐1,3‐phenylene)bis(oxy)]dibenzoic acid has been structurally characterized and the magnetic properties of the GdIII complex and the luminescence properties of the PrIII, EuIII and GdIII complexes were investigated.