PHOTOINITIATION OF THE ANIONIC CONDENSATION REACTION IN 2-CHLOROACRYLONITRILE VIA THE CHARGE-TRANSFER BANDS OF THE CL-CENTER-DOT(2-CHLOROACRYLONITRILE)(1,2) CLUSTERS

The ion-molecule complexes Cl-.(2-chloroacrylonitrile)(n), n=1, 2, wer e used to study electron-induced reactions of solvent molecules initia ted by a charge-transfer transition of the cluster. Photoexcitation of the Cl-. 2-chloroacrylonitrile complex produces the radical anion of 2-chloroacrylonitrile (CAN), with expulsion of the Cl atom. Excitation of Cl-. (CAN)(2) yielded photofragments that indicate the occurrence of an addition reaction of the CAN(-) radical to the second CAN molecu le, where Cl is again ejected. This photochemistry corresponds to the chain propagation step in the polymerization of(CAN)(n)(-) clusters, a nd is sufficiently exothermic to sequentially eliminate HCl units.