{Reference Type}: Journal Article {Title}: Photochemical [2+4]-Dimerization Reaction from the Excited State. {Author}: Ahuja S;Baburaj S;Valloli LK;Rakhimov SA;Manal K;Kushwaha A;Jockusch S;Forbes MDE;Sivaguru J; {Journal}: Angew Chem Int Ed Engl {Volume}: 63 {Issue}: 4 {Year}: 2024 Jan 22 {Factor}: 16.823 {DOI}: 10.1002/anie.202316662 {Abstract}: Aryl-maleimides undergo a novel [2+4]-photodimerization instead of the expected [2+2]-photodimerization under both direct irradiation with visible light and under sensitized energy transfer conditions. This new excited state reactivity in aryl-maleimides is deciphered through photochemical, photophysical, and spectroscopic studies. The stereochemistry of the photodimer depends on the type of non-bonding interactions prevalent during photodimerization which is in turn dictated by the substituents on the maleimide ring. More importantly, the stereochemistry of the photodimer formed is complementary to the product observed under thermal conditions.