 Abstract modern cells are complex chemical compartments tightly regulated by an underlying DNA encoded program. To achieve a form of coupling between molecular content, chemical reactions, and chassis and synthetic compartments, researchers have designed co-acivate droplets that promote non-enzymatic oligonucleotide polymerization and restructuring as a result of reaction dynamics. These co-acivates can be manipulated through light-induced trans-CIS as a benzene photoisomerization to demonstrate cycles of light-actuated oligonucleotide ligation. This tight coupling between reaction and structure provides a general root to the non-enzymatic synthesis of polynucleotides and paves the way for the emergence of a primitive compartment content coupling in membrane-free protocells. This article was authored by Tomosso P. Fraccia and Nicholas Martin.