Topological polymorphism and temperature-driven topotactic transitions of metal–organic coordination polymers

Abstract

Two metal-organic frameworks (MOFs) [Mg3(btdc)3(dmf)4]·DMF, (1) and [Mg3(btdc)3(dmf)4], (2) (H2btdc = 2,2´-bithiophen-5,5´-dicarboxylic acid; dmf = N,N-dimethylformamide) were synthesized from a similar reaction mixture at 80 °C or 130 °C, respectively....

Synthesis, supramolecular isomerism, and photoluminescence of scandium(iii) complexes with a tetrafluoroterephthalate ligand

“…In turn, this leads to the change from a discrete anionic scandium complex to the layered coordination polymer. A similar trend is observed for the syntheses of CPs based on Co(II) and succinate, 47,48 Cd(II) and terephthalates, 49 Mg(II) and 2,2′-bithiophene-5,5′-dicarboxylate, 50 and Cd(II) and octafluorobiphenyl-4,4′-dicarboxylate. 51 Fluorine contacts play an important role in the crystal engineering of fluorine-containing materials.…”

Phase engineering of metal‐organic frameworks

“…[78] It has been reported that the Mg 3 (RCOO) 6 building units can be linked by the linear 2,2′-bithiophen-5,5′-dicarboxylate (H 2 BTDC) ligand to synthesize two 3D MOFs with different structures via a temperature-controlled crystallization process. [79] As a result, the [Mg 3 (BTDC) 3 (DMF) 4 ]⋅DMF with a common pcu (low-temperature phase) and [Mg 3 (BTDC) 3 (DMF) 4 ] with a rare sxb (six-coordinated net, b type [80,81] ) (hightemperature phase) have been prepared by tuning the orientation of btdc 2anions under different reaction temperatures. Specifically, the [Mg 3 (BTDC) 3 (DMF) 4 ]⋅DMF and [Mg 3 (BTDC) 3 (DMF) 4 ] feature the parallel and semi-parallel arrangement of the btdc 2linkers, respectively.…”

Coordination Polymers of Scandium(III) and Thiophenedicarboxylic Acid

“…Compounds I and II have an identical formula of the coordination framework and are polymorphous modifications. A comparison of their crystallization conditions and structures shows a regularity often observed for other MOF: a lower synthesis temperature results in looser structures compared to those formed at higher temperatures, which lead, as a rule, to the formation of more compact phases with lower porosity [25][26][27]. Indeed, the low-temperature phase I has the crystallographic density of the framework ρ = 0.97 g/cm 3 and the pore volume equal to 56.7%, whereas the high-temperature phase II has the density ρ = 1.42 g/cm 3 and the pore volume equal to 31.8%.…”