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By applying caged thymidine residues, DNA duplexes were created in which Hg II ‐mediated base pair formation can be triggered by irradiation with light. When a bidentate ligand was used as the complementary nucleobase, an unprecedented stepwise formation of different metal‐mediated base pairs was achieved.

Light‐Induced Formation of Thymine‐Containing Mercury(II)‐Mediated Base Pairs