Molecular Design of Silicon-Containing Diazenes: Absorbance of E and Z Isomers in the Near-Infrared Region

The effective use of photochromic systems based on azo compounds in a number of applications, especially biomedical and pharmacological ones, is impeded by the unresolved problem of their E⇆Z isomerization in the near-IR region, NIR (780–1400 nm). We have demonstrated at the TD-DFT, STEOM-DLPNO-CCSD and CASSCF-NEVPT2 levels of theory that the presence of a silylated diazene core −Si−N=N−Si− with three-, tetra- or five-coordinated silicon atoms practically guarantees the absorption of the E and Z forms of such derivatives in NIR and the amazing (185–400 nm) separation of their first absorption bands. In particular, the maximum λ₁ of the first n→π* band of the E isomer of azosilabenzene ASiB is at ∼1030 nm, while for the Z isomer λ₁≅1340 nm. Based on the found bistable azo compounds ( ASiB , bis(silyl)- SiD and bis(silatranyl)- SaD diazenes) and their derivatives with E and Z absorption in NIR, unique photoswitches can be created for a number of applications, in particular, for photothermal therapy.