Mechanistically Different Mechanochromophores Enable Calibration and Validation of Molecular Forces in Glassy...

Sterically distorted donor-acceptor π-systems, termed DA springs, can be progressively planarized under mechanical load causing a bathochromic shift of the photoluminescence (PL) spectrum. By combining theory and experiment, we here use a simple linear force calibration for two different conformational mechanochromophores to determine molecular forces in polymers from the mechanochromic shift in PL wavelength during multiple uniaxial tensile tests. Two systems are used, i) a highly entangled linear glassy polyphenylene and ii) a covalent elastomeric polydimethylsiloxane network. The mean forces estimated by this method are validated using known threshold forces for the mechanochemical ring-opening reactions of two different spiropyran force probes. The agreement between both approaches underlines that these DA springs provide the unique opportunity for the online monitoring of local molecular forces present in diverse polymer matrices.