The role of thermodynamically stable configuration in enhancing crystallographic diffraction quality of flexible MOFs.

Single-crystal X-ray diffraction (SCXRD) is a widely used method for structural characterization. Generally, low temperature is of great significance for improving the crystallographic diffraction quality. Herein we observe that this practice is not always effective for flexible metal-organic frameworks (f-MOFs). An abnormal crystallography, that is, more diffraction spots at a high angle and better resolution of diffraction data as the temperature increases in the f-MOF (1-g), is observed. XRD results reveal that 1-g has a reversible anisotropic thermal expansion behavior with a record-high c-axial positive expansion coefficient of 1,401.8 × 10-6 K-1. Calculation results indicate that the framework of 1-g has a more stable thermodynamic configuration as the temperature increases. Such configuration has lower-frequency vibration and may play a key role in promoting higher Bragg diffraction quality at room temperature. This work is of great significance for how to obtain high-quality SCXRD diffraction data.

A cadmium(II) coordination polymer with both polyrotaxane and polycatenane features constructed by a V-shaped semi-rigid ligand: synthesis and fluorescence properties.

One of the most interesting phenomena in coordination polymers (CPs) is the co-existence of different interlaced motifs. However, CPs having two different interlaced motifs at the same time are still rare. Colourless block-shaped crystals of the two-dimensional polymer poly[[aqua(µ2-naphthalene-2,6-dicarboxylato){µ2-4,4'-[oxybis(4,1-phenylene)]dipyridine}cadmium(II)] monohydrate], {[Cd(C12H6O4)(C22H16N2O)(H2O)]·H2O}n, (I), was synthesized under hydrothermal conditions by the self-assembly of 4,4'-[oxybis(4,1-phenylene)]dipyridine (OPY) with CdII in the presence of naphthalene-2,6-dicarboxylic acid (H2ndc). Each CdII ion is six-coordinated by two N atoms from the pyridine rings of two OPY ligands and by four O atoms, three of which are from two ndc2- ligands and one of which is from a water molecule. In (I), every two identical two-dimensional (2D) 63 layers are interpenetrated in a parallel fashion, resulting in an interesting 2D→2D framework with both polyrotaxane and polycatenane characteristics. The extension of these sheets into a three-dimensional supramolecular net is via O-H...O hydrogen bonds. The solid-state photoluminescence properties of (I) are also discussed.