Stronger chemical bonds withstand higher mechanical forces; thus, the rupture of single bonds is preferred over the rupture of double or triple bonds or aromatic rings. We investigated bond scission in poly(dialkyl-p-phenylene ethynylene)s (PPEs), a fully conjugated polymer. In a scale-bridging approach using electron-paramagnetic resonance spectroscopy and gel permeation chromatography of cryomilled samples, in combination with density functional theory calculations and …