Selective Heavy Atom Effect Forming Photosensitizing Hot Spots in Double-Stranded DNA Matrix

Triplet exciton formation is essential for photosensitization-based photochemistry and photobiology. The heavy atom effect (HAE), in the form of either external or internal mode, is a basic mechanism for increasing the triplet exciton yield of photosensitizers. Herein, we report a new HAE mode by noncovalent cohosting of heavy atoms and photosensitizers in a double-stranded DNA (dsDNA) matrix. With dsDNA bearing several thymine (T) or cytosine (C) mismatches, heavy atoms (e.g., Hg²⁺ or Ag⁺) and dsDNA-staining dyes (photosensitizers) were spatially adjoined in close proximity, thus resulting in enhanced phosphorescence and ¹O₂ generation from the photosensitizers. The dsDNA-hosted HAE provides highly selective recognition for the heavy atoms, which is not applicable in either the external or the internal mode. Considering the simpleness and efficiency of the spatially adjoined HAE, as well as the functionality of DNA, the proposed HAE mode is appealing for various singlet oxygen- and phosphorescence-related applications.