Metal Organic Frameworks Assembled from Y(III), Na(I), and Chiral Flexible-Achiral Rigid Dicarboxylates

Abstract

New chiral metal organic frameworks, assembled from Y(III), Na(I), and chiral flexible-achiral rigid dicarboxylate ligands, formulated as [NaY(Tart)(BDC)(H2O)2] (1) and [NaY(Tart)(biBDC)(H2O)2] (2) (H2Tart = Tartaric acid; H2BDC = Terephthalic acid; H2biBDC = Biphenyl-4,4′-dicarboxylic acid), were obtained as single phases under hydrothermal conditions. Their structures were solved by single-crystal X-ray diffraction (XRD), and characterized by 13C CPMAS NMR, thermal analyses (thermogravimetry-mass spectrometry (TG-MS) and differential scanning calorimetry (DSC)), and X-ray thermodiffractometry. Both compounds crystallize in the orthorhombic chiral space group C2221 with a = 6.8854(2) Å, b = 30.3859(7) Å, c = 7.4741(2) Å for 1, and a = 6.8531(2) Å, b = 39.0426(8) Å, c = 7.4976(2) Å for 2. 1 and 2 are layered structures whose three-dimensional stability is ensured by strong hydrogen bond interactions. The dehydration of both compounds is accompanied by phase transformation, while the spontaneous rehydration process is characterized by different kinetics, fast in the case of 1 and slow for 2.