The photochemical trans → cis and thermal cis → trans isomerization pathways of azobenzo-13-crown ether: A computational study on a strained cyclic azobenzene system

The isomerization of azobenzo-13-crown ether can be expected to be hindered due to the polyoxyethylene linkage connecting the 2,2′-positions of azobenzene. The mixed reference spin-flip time-dependent density functional theory results reveal that the planar and rotational minima of the first photo-excited singlet state (S1) of the trans-isomer pass through a barrier (2.5–5.0 kcal/mol) as it goes toward the torsional conical intersection (S0/S1) geometry (