Abstract

The stimuli-induced gelation of a urethane-functionalized ditopic ureidopyrimidinone (UPy) compound is presented, and the mechanism by which the gelation proceeds is proposed. In a 40–120 mM solution in chloroform, the compound can exist in two different aggregated states, namely a low viscous mixture of (cyclic) oligomers or a fibrous gel. As evidenced by IR, NMR, and WAXS, the liquid state is stabilized by hydrogen bonds between the UPy and the back-folded chain, while the fibrous gel is stabilized by lateral hydrogen bonds within stacked UPy dimers. Controlled preparation techniques allow for pathway selection to arrive at one of both states. The remarkable long-term stability of the low viscous state (over 2 months for a 80 mM solution) is in contrast to the fast transformation into a gel by stirring in a few hours. Other mechanical stimuli like shaking, sonicating, and stirring for a shorter period, as well as freezing and thawing the solution, yield weaker gels than those obtained by long stirring. Heating the gels and slow cooling reversibly yield the nonviscous solution. This shows that the formation of UPy–urethane hydrogen bonds kinetically traps the UPy polymers, thereby preventing their lateral aggregation. The application of mechanical stress or freezing disrupts this interaction, allowing for the formation of a stacked nucleus on which further material can grow, eventually leading to gelation of the solution.

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