cg801138e_si_002.cif (13.18 kB)

Anion-Induced Formation of Lanthanide-Organic Chains From 3D Framework Solids. Anion Exchange in a Crystal-to-Crystal Manner

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posted on 06.05.2009 by Adonis Michaelides, Stavroula Skoulika
A water-mediated transformation reversibly converts the neutral 3D microporous coordination polymers [Ln2(adipate)3(H2O)4]·6H2O (Ln3+ = Pr3+) and [Ln2(adipate)3(H2O)4]xH2O (Ln3+ = Gd3+, Sm3+), into the ionic 1D polymer [Ln(adipate)(H2O)5]XH2O (with X = NO3, Cl and Ln3+ = Pr3+, Gd3+, Sm3+). The 1D polymer consists of positively charged hydrogen-bonded lanthanide−adipate chains enclathrating NO3 or Cl anions acting as templates. The hydrogen bonds linking the chains between them are so strong that it is possible to exchange NO3 for Cl and vice versa in a crystal-to-crystal manner. The anion exchange reactions were directly observed on crystals by using Raman microprobe spectroscopy, single-crystal X-ray diffraction, and scanning electron microscopy.