Mechanochromism of polyurethane based on folding–unfolding of cyano-substituted oligo(<i>p</i>-phenylene) vinylene dimer

doi:10.1007/s11706-023-0640-1

Front. Mater. Sci.

2023, Vol. 17

Issue (2) : 230640 https://doi.org/10.1007/s11706-023-0640-1

RESEARCH ARTICLE

Mechanochromism of polyurethane based on folding–unfolding of cyano-substituted oligo(p-phenylene) vinylene dimer

Na Zhang^1,², Xiang-Yu Ma^1,², Shun Li^1,², Yu-Xin Zhang^1,², Chen Lv^1,², Zheng-Peng Mao^1,², Zi-Yi Dou^1,², Tai-Sheng Wang^1,²(

)

¹. School of Materials Science and Engineering, Nanjing Institute of Technology, Nanjing 211167, China
². Jiangsu Key Laboratory of Advanced Structural Materials and Application Technology, Nanjing 211167, China

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Abstract

The incorporation of mechanophores, motifs that transform mechanical stimulus into chemical reaction or optical variation, allows creating materials with stress-responsive properties. The most widely used mechanophore generally features a weak bond, but its cleavage is typical an irreversible process. Here, we showed that this problem can be solved by folding–unfolding of a molecular tweezer. We systematically studied the mechanochromic properties of polyurethanes with cyano-substituted oligo(p-phenylene) vinylene (COP) tweezer (DPU). As a control experiment, a class of polyurethanes containing only a single COP moiety (MPU) was also prepared. The DPU showed prominent mechanochromic properties, due to the intramolecular folding–unfolding of COP tweezer under mechanical stimulus. The process was efficient, reversible and optical detectable. However, due to the disability to form either intramolecular folding or intermolecular aggregation, the MPU sample was mechanical inert.

Keywords mechanochromism molecular tweezer folding–unfolding cyano-substituted oligo(p-phenylene) vinylene polyurethane

Corresponding Author(s): Tai-Sheng Wang

Issue Date: 13 March 2023

Cite this article:

Na Zhang,Xiang-Yu Ma,Shun Li, et al. Mechanochromism of polyurethane based on folding–unfolding of cyano-substituted oligo(p-phenylene) vinylene dimer[J]. Front. Mater. Sci., 2023, 17(2): 230640.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-023-0640-1
https://academic.hep.com.cn/foms/EN/Y2023/V17/I2/230640

Fig.1 Schematic diagram of molecular comformation changes of (a) DPU-0.2 and (b) MPU-0.2 films under force (also shown were fluorescent images of DPU-0.2 and MPU-0.2 upon 0% and 300% strains). (c) Chemical structures of MCOP and DCOP. (d) Synthetic routes for DPU-m and MPU-n.

Tab.1 Number-average molecular weight (M_n), weight-average molecular weight (M_w), and polydispersity index (PDI) of synthesized polymers

Fig.2 (a) UV-visible absorption spectra of DCOP and MCOP in the THF solution (c = 5 μmol·L^?1). (b) Fluorescent spectra of DCOP and MCOP in the THF solution (c = 5 μmol·L^?1, λ_ex = 365 nm). The inserts showed images of MCOP and DCOP under ambient light (panel (a)) and 365 nm UV light (panel (b)).

Fig.3 Fluorescent spectra of (a) DCOP and (b) MCOP in THF with different concentrations (λ_ex = 365 nm). Absorption spectra of (c) DCOP and (d) MCOP in THF with different concentrations.

Fig.4 (a) Images of DPU-0.2 and MPU-0.2 under UV light and visible light. Fluorescence decay profiles of (b) DPU-0.2 and (c) MPU-0.2 films.

Fig.5 Normalized fluorescent spectra of (a) DPU and (b) MPU films.

Fig.6 (a)(b) Stress–strain curves of DPU films and MPU films. (c) Normalized fluorescent spectra of DPU-0.2 film with the increasing strain (the insert showed fluorescent images of DPU-0.2 film under 0% and 100% strains). (d) Normalized fluorescent spectra of MPU-0.2 film with the increasing strain (the insert showed fluorescent images of MPU-0.2 film under 0% and 300% strains). (e) Variation of the I₅₁₀/I₅₅₀ emission ratio of DPU-0.2 with the strain. (f) Variation of the I₅₁₀/I₅₅₀ emission ratio of DPU-0.2 film with the temperature.

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