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)(H(2)O)(2)] (1) and [NaY(Tart)(biBDC)(H(2)O)(2)] (2) (H(2)Tart = Tartaric acid; H(2)BDC = Terephthalic acid; H(2)biBDC = 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 (13)C 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 C222(1) with a = 6.8854(2) A, b = 30.3859(7) A, c = 7.4741(2) A for 1, and a = 6.8531(2) A, b = 39.0426(8) A, c = 7.4976(2) A 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.

Metal–organic frameworks assembled from lanthanide and 2,5-pyridinedicaboxylate with cubane-like [Ln4(OH)4] building units

“…In continuation of our previous works concerning the synthesis and characterization of LOFs based on flexible [38], rigids [15,22], and rigid-flexible dicaboxylate ligands [16,18] Single-Crystal X-Ray Diffraction Studies. For 25pYb and 25pY-2 samples (not suitable single-crystal in the case of 25pY-1), data collection was performed at 293 K on an Agilent Gemini CCD diffractometer, using CuKĮ radiation.…”

“…Recently, much work has been focused on lanthanide-containing MOFs (LOFs) [14][15][16], because these compounds give rise to luminescence materials [17][18][19][20][21][22][23], with increased brightness and emission quantum yield [24,25], and therefore they could be very promising class of materials in a wide range of optical applications including fluorescent sensing [26][27][28], imaging contrast agents [29,30], and lighting and displays [31]. Many d-block transition metal cations prefer to be coordinated by soft donor atoms, whereas lanthanide cations (Ln 3+ ), with their high and variable coordination numbers and flexible coordination environments, have high affinity for hard donor atoms [32,33], and therefore leading to complex network topologies with promising potential applications.…”

Chiral Lanthanide Metal-Organic Frameworks

“…Amghouz et al [65,66] layered chiral structures built up by mixing Ln(III), Na(I), and chiral flexibleachiral rigid dicarboxylate ligands, and crystallize in the orthorhombic chiral space group C222 1 . In each compound, the Ln(III) cation is bonded to eight oxygen atoms, six of them are from carboxylic groups and two are from hydroxyl groups.…”

Light-emitting lanthanide-based organic–inorganic hybrids

“…This material exhibits strong negative linear thermal expansion along the c direction due to framework flexibility [1]. In situ, single-crystal and powder x-ray diffraction under high pressure in diamond anvil cells indicate that the c lattice parameter increases by 8% from ambient pressure up to 1.8 GPa, which is the highest negative linear compressibility (NLC) known for any material.…”

“…A significant change occurs in the Au sublattice with the Au-Au interatomic vector becoming canted with respect to c. This provides an additional compression mechanism, which reduces the need for the structure to expand along c. These results provide a detailed structural mechanism for the exceptional and unusual mechanical properties of this material. [1] Goodwin [1][2][3][4][5]. The compounds have been studied by single-crystal and powder X-ray diffraction, X-ray powder thermodiffractometry, thermal analyses (TG-MS and DSC), vibrational spectroscopy (FTIR), scanning and transmission electron microscopy (SEM-EDX and TEM), and elemental analysis.…”