Lanthanide-based molecular alloys with hydroxyterephthalate: a versatile system

• Published in: CrystEngComm 2021-01, Vol.23 (1), p.1-118
• Main Authors: Wang, Jinzeng, Suffren, Yan, Daiguebonne, Carole, Bernot, Kevin, Calvez, Guillaume, Freslon, Stéphane, Guillou, Olivier
• Format: Article
• Language: English
• Subjects: Aqueous solutions; Chemical compounds; Chemical Sciences; Coordination polymers; Crystal growth; Crystal structure; Crystallinity; Crystallography; Diffusion rate; Evaporation; Gadolinium; Gels; Optical measurement; Optical properties; Polymers; Single crystals; X ray powder diffraction
• ISSN: 1466-8033; 1466-8033
• DOI: 10.1039/d0ce00947d

Reactions in water between lanthanide chlorides and the disodium salt of 2-hydroxyterephthalic acid (H 2 hbdc) lead to six families of lanthanide-based coordination polymers depending on the lanthanide ion and the crystal growth method. Compounds that constitute family F1 have the general chemical formula [Ln(Hhbdc)(hbdc)·9H 2 O] ∞ with Ln = La-Nd and have been obtained by slow evaporation. [Ln 2 (hbdc) 3 (H 2 O) 6 ·4H 2 O] ∞ with Ln = Sm-Eu constitute family F2 and have been obtained by solvothermal synthesis. Family F3 includes compounds, obtained by a solvothermal method, with the general chemical formula [Ln 2 (hbdc) 3 (H 2 O) 4 ·4H 2 O] ∞ with Ln = Ho-Lu plus Y and compounds obtained by slow diffusion through gels with Ln = Eu-Tb. [Ln(Hhbdc)(hbdc)(H 2 O) 3 ·H 2 O] ∞ with Ln = Tb-Dy have been obtained by solvothermal methods and constitute family F4 . [Gd 2 (hbdc) 3 (H 2 O) 8 ·6H 2 O] ∞ ( F5 ) has been obtained by slow evaporation. The last family ( F6 ) includes compounds with the general chemical formula [Ln 2 (hbdc) 3 (H 2 O) 8 ·2H 2 O] ∞ with Ln = Nd-Tb that have been obtained by slow diffusion through gel media. Gd-Based micro-crystalline powders can be obtained by direct mixing of aqueous solutions of Gd 3+ and hbdc 2− . Unexpectedly, the micro-crystalline powder belongs to F5 when the lanthanide solution is added to the ligand one and to F6 when the opposite occurs. This phenomenon is also observed for the Tb- and/or Eu-based heterolanthanide coordination polymers. Their optical properties have been studied in detail. Reactions in water between lanthanide chlorides and the di-sodium salt of 2-hydroxyterephthalic acid (H 2 hbdc) lead to six families of lanthanide-based coordination polymers depending on the lanthanide ion and the crystal growth method.