Reversible chemistry of CO2 in the preparation of fluorescent supramolecular polymers

The chemistry between CO(2) and primary amines was used to construct novel types of supramolecular polymers and networks. Fluorescent self-assembling gel 2 was prepared, which employs both hydrogen bonding and dynamic, thermally reversible carbamate bonds. As precursors, biscalixarenes 1, 3, 4, 6, and 7 were synthesized, which strongly aggregate (K(D) > or = 10(6) M(-1) per capsule) in apolar solution with the formation of linear self-assembling polymers. Polymer 1n possesses CO(2)-philic primary amino groups on the periphery. CO(2) rapidly reacts with chains 1n in apolar solvents and cross-links them with the formation of multiple carbamate salt bridges. Three-dimensional polymeric network 2 was characterized by (13)C NMR spectroscopy and SEM. Addition of competitive solvent breaks hydrogen bonding in 2 but does not influence the carbamate linkers. Carbamate salt 9 was obtained. On the other hand, thermal release of CO(2) from 2 and 9 was easily accomplished (1 h, 100 degrees C) with retaining the hydrogen-bonding capsules. Thus, three-dimensional polymeric networks 2 were transformed back to linear polymeric chains 1n without their breakup. Multiple pyrene fluorophores, attached on the periphery of 2, cause strong fluorescence of the gel with benzene. When approximately 5% nitrobenzene was gelated together with benzene, fluorescence strongly decreases due to the energy transfer from the pyrene donors in gel 2 to trapped nitrobenzene molecules. This opens a way to switchable fluorescent materials.