Polymer Mechanochromism from Force-Tuned Excited-State Intramolecular Proton Transfer

• Published in: Journal of the American Chemical Society Vol. 144; no. 22; pp. 9971 - 9979
• Main Authors: Hu, Huan, Cheng, Xin, Ma, Zhimin, Sijbesma, Rint P., Ma, Zhiyong
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 08-06-2022
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.2c03056

Real-time monitoring of strain/stress in polymers is a big challenge to date. Herein, we for the first time report an ESIPT (excited-state intramolecular proton transfer)-based mechanochromic mechanophore (MM). The synthesis of target MM PhMz-4OH [(2-hydroxyphenyl)­benzimidazole with four aliphatic hydroxyls] is quite facile. PhMz-4OH possesses characteristic dual emissions, and its ESIPT activity is greatly affected by steric hindrance. Then, PhMz-4OH was covalently linked into polyurethane chains (PhMz-4OH@PU). Upon stretching, the PhMz-4OH@PU films showed fluorescence color change and spectral variation with the increase in enol emission and blueshift of keto emission due to the force-induced torsion of the dihedral angle between the proton donor and the proton acceptor. The PhMz-4OH@PU films with high mechanophore concentrations (>0.36 mol %) might undergo a two-stage force-responsive process, including torsion of the dihedral angle via force-induced disaggregation and direct chain-transduced force-induced torsion of the dihedral angle. The intensity ratio of enol emission to keto emission (I E/I K) shows a quantitative correlation with elongation, and real-time strain sensing is achieved. PhMz-4OH is a successful type II MM (without covalent bond scission) and displays high sensitivity and excellent reversibility to stress. Two control structures PhMz-NH2 and PhMz-2OH were also embedded into PU but no spectral or color changes were detected, further confirming that mechanochromism of PhMz-4OH@PU films arises from the chain-transduced force. Density function theory (DFT) calculation was performed to study the force-tuned ESIPT process theoretically and rationalize the experimental results. This study might lay the foundation for real-time stress/strain sensing in practical applications.