Ultrafast intersystem-crossing in platinum containing π-conjugated polymers with tunable spin-orbit coupling

The development of efficient organic light-emitting diodes (OLED) and organic photovoltaic cells requires control over the dynamics of spin sensitive excitations. Embedding heavy metal atoms in π-conjugated polymer chains enhances the spin-orbit coupling (SOC), and thus facilitates intersystem crossing (ISC) from the singlet to triplet manifolds. Here we use various nonlinear optical spectroscopies such as two-photon absorption and electroabsorption in conjunction with electronic structure calculations, for studying the energies, emission bands and ultrafast dynamics of spin photoexcitations in two newly synthesized π-conjugated polymers that contain intrachain platinum (Pt) atoms separated by one (Pt-1) or three (Pt-3) organic spacer units. The controllable SOC in these polymers leads to a record ISC time of <∼1a ...ps in Pt-1 and ∼6a ...ps in Pt-3. The tunable ultrafast ISC rate modulates the intensity ratio of the phosphorescence and fluorescence emission bands, with potential applications for white OLEDs.