CO2 in supramolecular chemistry: preparation of switchable supramolecular polymers

CO2 gas was used to construct novel types of supramolecular polymers. Self-assembling nanostructures 11 and 13 were prepared, which employ both hydrogen bonding and dynamic, thermally reversible carbamate bonds. As precursors, calixarene ureas 1 and 2 were synthesized, which strongly aggregate/dimerize (K(D)>/=10(6) M(-1) per capsule) in apolar solution with the formation of self-assembling capsules 7 and linear polymeric chains 8, respectively, and also possess "CO2-philic" primary amino groups on the periphery. CO2 effectively reacts with molecules 7 and 8 in apolar solvents and cross-links them with the formation of multiple carbamate salt bridges. Oligomeric aggregate 11 and three-dimensional polymeric network 13 were prepared and characterized by 1H and 13C NMR spectroscopy. The morphology of supramolecular gel 13 was studied by scanning electron microscopy. Addition of a competitive solvent destroyed the hydrogen bonding in assembling structures 11 and 13, but did not influence the carbamate linkers; carbamate salts 12 and 14, respectively, were obtained. On the other hand, thermal release of CO2 from 11 and 13 was easily accomplished (1 h, 100 degrees C) while retaining the hydrogen-bonding capsules. Thus, three-dimensional polymeric network 13 was transformed back to linear polymeric chain 8 without breaking up. Encapsulation and storage of solvent molecules by 11 and 13 was demonstrated. This opens the way for switchable materials, which reversibly trap, store, and then release guest molecules. A two-parameter switch and control over hydrogen bonding and CO2-amine adducts was established.