Dipyrene-Terminated Oligosilanes Enable Ratiometric Fluorescence Response in Polymers toward Mechano- and...

Developing fluorescent motifs capable of displaying mechano- and thermo-stimuli reversibly and ratiometrically is appealing for monitoring the deformation or temperature to which polymers are subjected. Here, a series of excimer-type chromophores Si-Py (n = 1-3) consisting of two pyrenes linked with oligosilanes of one to three silicon atoms is developed as the fluorescent motif incorporated in a polymer. The fluorescence of Si-Py is steered with the linker length where Si₂-Py and Si₃-Py with disilane and trisilane linkers display prominent excimer emission accompanied by pyrene monomer emission. Covalent incorporation of Si₂-Py and Si₃-Py in polyurethane gives fluorescent polymers PU-Si₂-Py and PU-Si₃-Py, respectively, where intramolecular pyrene excimers and corresponding combined emission of excimer and monomer are obtained. Polymer films of PU-Si₂-Py and PU-Si₃-Py display instant and reversible ratiometric fluorescence change during the uniaxial tensile test. The mechanochromic response arises from the reversible suppression of excimer formation during the mechanically induced separation of the pyrene moieties and relaxation. Furthermore, PU-Si₂-Py and PU-Si₃-Py show thermochromic response toward temperature, and the inflection point from the ratiometric emission as a function of temperature gives an indication of the glass transition temperature (T_g) of the polymers. The design of the excimer-based mechanophore with oligosilane provides a generally implementable way to develop mechano- and thermo-dual-responsive polymers.