Abstract: | Four tetraphenylethylenes ( 2 a – d ) containing an electron‐rich 2,3,4,6‐tetrahydro‐1,6‐dithia‐3a‐azaphenalene (THDTAP) moiety have been synthesized. The 2 a – d show aggregation‐induced emission (AIE) with yellowish green photoluminescence (PL) in THF‐H2O (v/v, 1:9) solution and in the solid state. Compounds 2 a – d undergo 1,2‐migratory shift in oxidative cyclodehydrogenation reactions to afford the unexpected products 3 a – d which display green PL in CH2Cl2 solution and are non‐emissive in the solid state. The PL intensities of 3 a – d are clearly enhanced in the presence of meta‐chloroperoxybenzoic acid (mCPBA) owing to the oxidation of the S‐atoms on the THDTAP moiety. In contrast, the PL of 2 a – d in THF‐H2O (v/v, 1:9) solution is quenched by adding mCPBA, ascribable to the oxidation of the C=C bond on the ethylene moiety. It is found that the absorption of 3 a – d is distinctly red‐shifted from the UV/Vis region to the NIR region upon acidification, arising from the protonation of the N‐atom on the THDTAP moiety. Furthermore, 3 a – d display nonlinear optical response (NLO) and optical limiting (OL) behaviour which is superior to that of the well‐known OL material C60. |