Coordinative-to-Covalent Transformation, Isomerization Dynamics, and Logic Gate Application of Dithienylethene Based Photochromic Cages

Photochromic coordinative cages containing dynamic C=N imine bonds are assembled from dithienylethene-based aldehyde and tris-amine precursors via metallo-component self-assembly. The resulting metal-templated cages are then reduced and demetalated into pure covalent-organic cages (COCs), which are otherwise difficult to prepare via de novo organic synthesis. Both of the obtained coordinative and covalent cages can be readily interconverted between the ring-open (o-isomer) and the one-lateral ring-closed (c-isomer) forms by UV/vis light irradiation, demonstrating distinct absorption, luminescence and photoisomerization dynamics. Specifically, the ring-closed c-COCs show blue-shifted absorption band compared with analogous metal-templated cages, which can be applied in photoluminescence (PL) color-tuning of upconversion materials in different way, showing potentials to construct multi-readout logic gate systems.