Conformer Ring Flip Enhances Mechanochromic Performance of ansa-Donor–Acceptor–Donor Mechanochromic Torsional Springs

化学 噻吩 连接器 化学机械平面化 环应变 接受者 力谱学 戒指(化学) 结晶学 光化学 分子 有机化学 凝聚态物理 图层(电子) 物理 操作系统 计算机科学
作者
Raphael Hertel,Wafa Maftuhin,Michael Walter,Michael Sommer
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:144 (48): 21897-21907 被引量:18
标识
DOI:10.1021/jacs.2c06712
摘要

Mechanochromophores based on conformational changes of donor-acceptor-donor (DAD) springs allow sensing of forces acting on polymer chains by monotonic changes of absorbance or photoluminescence (PL) wavelength. Here, we identify a series of thiophene (D)-flanked quinoxalines (A) as molecular torsional springs for force sensing in bulk polymers at room temperature. The mode of DAD linkage to the polymer matrix and linker rigidity are key parameters that influence the efficacy of force transduction to the DAD spring and thus mechanochromic response, as probed by in situ PL spectroscopy of bulk films during stress-strain experiments. The largest shift of the PL maximum, and thus the highest sensitivity, is obtained from an ansa-DAD spring exhibiting bridged D units and a stiff A linker. Using detailed spectroscopy and density functional theory calculations, we reveal conformer redistribution in the form of a thiophene ring flip as the major part of the overall mechanochromic response. At forces as low as 27 pN at early stages of deformation, the ring flip precedes mechanically induced planarization of the ansa-DAD spring, the latter process producing a PL shift of 21 nm nN-1. Within the stress-strain diagram, the thiophene ring flip and DAD planarization are thus two separated processes that also cause irreversible and reversible mechanochromic responses, respectively, upon sample failure. As the thiophene ring flip requires much smaller forces than planarization of the DAD spring, such micromechanical motion gives access to sensing of tiny forces and expands both sensitivity and the force range of conformational mechanochromophores.
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