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Electronic-structure calculations combined with nonadiabatic trajectory surface-hopping (TSH) dynamic simulations were carried out on two alkenyl-substituted Criegee intermediates (CIs), i.e., propenyl-substituted CI (PCI) and 1-methyl-propenyl substituted CI (MPCI), in order to investigate the influence of the position and number of substituents on the photochemical process of CI in S1states. It is found that they play critical roles in the reactivity, dominant product channel, and mechanism of the CIs. More specifically, introducing a methyl group on either C1 (α-C) or C3 (γ-C) position of a vinyl-substituted CI (VCI) skeleton facilitates the rotation of the C1═O1 bond and leads to the formation of a three-membered dioxirane ring; meanwhile, it evidently enhances the reactively of the S1-state molecule. Meanwhile, methyl substitution on the vinyl moiety [i.e., C2 (β-C) and C3 (γ-C) positions] is beneficial for the rotation of the C2═C3 bond and thus facilitates the formation of the five-membered 1,2-dioxole ring, and the substitution on C2 site decreases the reactivity. The cosubstitution of C2 and C3 atoms by methyl groups well balances the features of VCI in the sense of high reactivity, consistently predominant channel, and possible dioxole side-product. The findings here not only deepen the knowledge on the photochemical processes of the CI but also inspire the rethinking of the “old” concept of substitution effect.

Photochromic phenylhydrazones are one of the most promising candidates for a photoswitchable fluorescent probe with potential applications in various fields, but mechanistic understanding of the origin of this unique behavior is limited. In this work, we explored the emission nature and switching mechanism of a model phenylhydrazone-based fluorescent photoswitch, DMA-PHA, by means of TD-DFT and CASPT2 calculations. The fluorescence-emitting Zconfiguration of DMA-PHA does not involve an excited-state intramolecular proton transfer process since the resonance effect between the DMA group and the rest part of the molecule in the excited state strengthens the hydrogen bond and thus stabilizes the emissive state. The light-induced fluorescence toggling results from E↔Zinterconversion driven by an out-of-plane C═N bond torsion and assisted by a N–N single bond rotation, which in total lead to a charge separation process losing the fluorescence activity. The N–N bond rotation in phenylhydrazone further enhances the competitive nonradiative decay and reduces the photoisomerization yields. The theoretical results will provide the guidance for the rational design of novel and improved photoswitchable fluorescent probes with desired performances.