Synthesis of Sidechain Free Hydrazone-Linked Covalent Organic Frameworks Through Supercritical Carbon Dioxide Activation

Supercritical carbon dioxide (scCO2) activation provides milder conditions to process covalent organic frameworks (COFs) without compromising their crystallinity and porosity. To this end, three hydrazone COFs (TFPB-DHz COF, TFPT-DHz COF, Py-DHz COF) were synthesized with a terephthaloyl dihydrazide linker (DHz) which has no substituents. To date, the synthesis of hydrazone COFs without a narrow range of alkoxy linkers has not been possible. The scCO2 activated hydrazone-linked COFs in this study were crystalline and had high surface areas (TFPB-DHz COF, TFPT-DHz COF and Py-DHz COF were 790 m²/g, 1199 m²/g, and 932 m²/g, respectively). This study shows the significance of using milder activation methods for making hydrazone-linked COF structures that were previously inaccessible.

Effect of Substituents of Cerium Pyrazolates and Pyrrolates on Carbon Dioxide Activation

Homoleptic ceric pyrazolates (pz) Ce(RR’pz)4 (R = R’ = tBu; R = R’ = Ph; R = tBu, R’ = Me) were synthesized by the protonolysis reaction of Ce[N(SiHMe2)2]4 with the corresponding pyrazole derivative. The resulting complexes were investigated in their reactivity toward CO2, revealing a significant influence of the bulkiness of the substituents on the pyrazolato ligands. The efficiency of the CO2 insertion was found to increase in the order of tBu2pz < Ph2pz < tBuMepz < Me2pz. For comparison, the pyrrole-based ate complexes [Ce2(pyr)6(µ-pyr)2(thf)2][Li(thf)4]2 (pyr = pyrrolato) and [Ce(cbz)4(thf)2][Li(thf)4] (cbz = carbazolato) were obtained via protonolysis of the cerous ate complex Ce[N(SiHMe2)2]4Li(thf) with pyrrole and carbazole, respectively. Treatment of the pyrrolate/carbazolate complexes with CO2 seemed promising, but any reversibility could not be observed.