A Synopsis on CO2 Capture by Synthetic Hydrogen Bonding Receptors.

Carbon dioxide (CO2) is one of the most abundant greenhouse gases in Earth's atmosphere and responsible for global warming. Therefore, aerial CO2 capture and sequestration has become a major task for human community. Though several adsorbents for CO2 including activated carbon, zeolites, metal-organic frameworks (MOFs), and other surface-modified porous materials are well developed, the supramolecular approaches using synthetic hydrogen-bonding receptors are less explored. This review article highlights the synthetic development of various artificial receptors and their properties toward fixation of aerial CO2 as carbonate (CO32-), bicarbonate (HCO3-), or carbamate (-NHCOO-/>NCOO-) ions, induced by excess fluoride (F-) or hydroxide (OH-) ions as their tetrabutylammonium salts. The utilization of encapsulated carbonate/bicarbonate/carbamate complexes in anion exchange metathesis for separation of oxyanions from aqueous solutions are also discussed. In addition, the release of CO2 and regeneration of receptor molecules are described in a number of occasions. Most importantly, the formation of anion complexes as crystalline materials in solid-state is described in terms of supramolecular chemistry and correlated with their solution-state properties. Finally, the types of receptors containing various functional groups are scrutinized in CO2 uptake, storage, and release processes and hints of endeavours for future research are delineated.

Does Larger Cavity-Size Really Help Bigger Anions to Bind? A Scrutiny on Core-Expanded Calix[4]pyrroles and Their Properties.

Calix[4]pyrroles are an important class of oligopyrrolic macrocycles and have found applications in many diverse fields including anion recognition. To modulate the properties of the calix[4]pyrrole, several structural modifications are realized. The core-expansion has attracted extra attention as it provides larger cavity-size compared to parent calix[4]pyrrole(s). This review highlights the synthetic development of various core-expanded calix[4]pyrroles and their applications in anion-binding properties. Emphasis is given to the changes in the binding properties observed with expanded versions of calix[4]pyrrole(s) in both solution and the solid states. The expanded versions of calix[4]pyrrole do not always show higher binding affinities for larger anions as anticipated. Rather, they display reduced affinities with the anions. The truncated form or asymmetric nature of the expanded versions of calix[4]pyrrole does not probably allow to access all the available binding sites for the anions and hence reduced binding affinities are observed. The receptors which contain a greater number of binding sites and are somehow rigid or preorganized apparently show enhanced binding affinities for anions. The relative binding constants for halide series indicate that the enlarged molecules are more beneficial for largest iodide among others. However, most of the receptors show selectivity towards smallest fluoride over other anions studied.