Modified from the work by Sanda et al. and Kottisch et al. , DOT (25-1000 equiv.) was dissolved in a suitable anhydrous solvent unless otherwise mentioned below. Stock solutions of different initiators (boron trifluoride etherate BF3•Et2O, methyl triflate MeOTf, tin(IV) chloride SnCl4, trifluoromethanesulfonic acid TfOH, methyl ptoluenesulfonate MeOTs, PCCP) (1 equiv.) were prepared in the same solvent and they were added to DOT. The mixture was stirred at RT for different time durations mentioned in Table . For experiments under O2-free conditions, each solution was sealed with a septum and degassed for 30 mins by bubbling nitrogen gas separately. For kinetics measurements, aliquots were withdrawn in intervals and quenched with a drop of methanol followed by NMR analysis of the crude mixture in CDCl3. The polymers were purified by precipitating into ice-cold hexane-diethyl ether (1:1 by volume, approximately 20-fold excess), centrifugation and drying in vacuum. Products presented as white solids and were dissolved in THF for SEC analysis. For experiments in different temperatures, the solutions were prepared as mentioned above and kept for stirring in an ice-cold bath or a salt-ice bath maintaining the required temperatures.