Lanthanide-Based Molecular Materials: Gel Medium Induced Polymorphism

• Published in: Crystal growth & design 2003-11, Vol.3 (6), p.1015-1020
• Main Authors: Daiguebonne, Carole, Deluzet, André, Camara, Magatte, Boubekeur, Kamal, Audebrand, Nathalie, Gérault, Yves, Baux, Christophe, Guillou, Olivier
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Inorganic chemistry
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/cg020060b

The reaction of Er3+ with polycarboxylate ligands in a gel medium frequently leads to coordination polymers that cannot be obtained via hydrothermal methods. A new Er3+ 1,2,4,5-benzenetetracarboxylate based coordination polymer, namely, Er4(C10H2O8)3(H2O)12·12H2O, has been synthesized and its crystal structure is reported herein. It crystallizes in the space group P1̄ (no. 2) with a = 10.4005(2) Å, b = 10.6486(2) Å, c = 13.6321(3) Å, α = 105.3070(7)°, β = 93.8348(8)°, γ = 108.9345(12)°, and Z = 2. To investigate the influence of the gel medium on the observed polymorphism, the Ni2+/1,3,5-benzenetricarboxylate system was studied, and polymorphism was also observed in this case. The crystal structure of a new Ni2+-containing coordination compound, namely, the Ni3(C9H3O6)2(H2O)14·4H2O, has been synthesized and its crystal structure is also reported. It crystallizes in the space group P1̄ (no. 2) with a = 6.6892(9) Å, b = 10.7615(15) Å, c = 12.3163(16) Å, α = 98.907(16)°, β = 102.171(16)°, γ = 108.074(16)°, and Z = 2. Its thermal behavior has also been studied and an hydration/dehydration cycle similar to the one already observed in the Er3+/1,3,5-benzenetricarboxylate is described. The availability for potential industrial applications of all the reported phases is discussed.