First, two experiments were done to facilitate "α-depolymerization". The proposed mechanism (Scheme 3, Pathway 1) requires the presence of an α thiocarboxylic acid, as expected for BF3•Et2O-initiated polymers (since the initiation occurs through protons formed with adventitious water). Thus, samples of BF3•Et2O-initiated pDOT and MeOTf-initiated pDOT (which, carrying a methyl thiocarboxylate α endgroup, was not expected to undergo α-depolymerization) were treated with 2,6lutidine. This base of low nucleophilicity was expected to efficiently deprotonate thiocarboxylic acid α end-groups. However, neither polymer showed any formation of DTO or changes in the SEC-measured molecular weight distribution. Next, a sample of BF3•Et2O-initiated pDOT was treated with 10 mol-% (relative to thioester linkages) of potassium thioacetate, a small molecular model of a thiocarboxylate α end-group. Only a negligible amount of DTO was formed. These experiments indicated that αdepolymerization does not play an important role in the degradation of pDOT. The absence of α thiocarboxylate-initiated self-immolation is also confirmed by the observed stability of BF3•Et2O-initiated pDOT samples during storage (see above).