Photoinduced Charge Separation Prompted Intervalence Charge Transfer in a Bis(thienyl)diketopyrrolopyrrole Bridged Donor-TCBD Push-Pull System

Intervalence charge transfer (IVCT), a phenomenon observed in molecular systems comprised of two redox centers differing in oxidation states by one unit, is reported in a novel, newly synthesized, multi-modular donor-acceptor system comprised of central bis(thienyl)diketopyrrolopyrrole (TDPP) hosting two phenothiazine-tetracyanobutadiene (PTZ-TCBD) entities on the opposite sides. One-electron reduction of TCBD promoted electron exchange between the two TCBD resulting in IVCT transition in the near-infrared region. The stabilization energy, - D G com and comproportionation equilibrium constant, K com calculated from peak potentials of the split reduction waves were found to be 1.06 x 10 4 J/mol, and 72.3 M -1 , respectively. Further, the IVCT transition was also witnessed during the process of thermodynamically feasible electron transfer upon excitation of the TDPP entity in the system, and served as a diagnostic marker to characterize the electron transfer product. Subsequent transient absorption spectral studies and data analysis by Global and Target analyses revealed occurrence of ultrafast charge separation (k cs ~ 10 10 s -1 ) owing to the close proximity and good communication between the entities of the multi-modular donor-acceptor system. The role of central TDPP in promoting IVCT is borne out from the present investigation.