Photomodulation of DNA‐Templated Supramolecular Assemblies

A new type of DNA ligand that contains a phosphate‐binding group and a photoresponsive azobenzene moiety is reported. When the azobenzene is in trans configuration, the ligand binds to the minor groove of a double‐stranded DNA, whereas it partially desorbs upon trans–cis isomerisation with light. The ability to photoswitch the ligand upon interaction with DNA is evidenced by (chir)optical signatures, and deciphered by the differences of binding geometry, stability, and dynamics of the DNA/ligand complexes for the two isomers. We exploit these properties to photomodulate DNA‐templated self‐assembly, through the incorporation of another π‐stacking DNA ligand, which together with the photoresponsive ligand form mixed supramolecular complexes along DNA. Our study demonstrates that well‐designed photoresponsive DNA binders can be used to modulate multicomponent supramolecular DNA assemblies