Oligomerization Driven by Phase Separation

Chemical reactions occurring within liquid-liquid phase separated systems drive numerous biological processes and have likely been involved in the emergence of first cellular compartments. Herein we report a reaction whose product distribution is drastically affected by the presence of a liquid-liquid interface. Under phase separated conditions, the system produces a dynamic library of increasingly complex oligomeric structures. This reactivity is in sharp contrast to results under homogeneous conditions; when there is no phase separation only two thermodynamically stable products are formed. The reactivity observed using phase separated conditions stems from generating a dynamic out-of-equilibrium self-assembling system. This work shows that relatively complex oligomeric products that would not be otherwise easily accessible can be made by biphasic out-of-equilibrium processes.