molecular details can be characterized in a visualized and quantitative way, not only will the alert of stress evolution and polymer failure be realized, but also fundamental insight in the molecular origins of toughness will be possible. [11][12][13] Over the past decade, polymer mechanochemistry has been recognized as a unique tool to bring about productive chemical reactions with a largely unexplored stimulusmechanical force, therefore is powerful in shedding light on how force is distributed within macromolecular structures. [14][15][16][17][18] Mechanofluorochromic hydrogels, which can indicate damage or excessive stress in highly polarized environments with a clearly perceptible optical signal, are potentially useful in a variety of biocompatible applications, such as bioimaging, stress sensor, optical storage, and biomechanics. [19][20][21][22][23][24][25] For this purpose, designing and engineering fluorochromic units ("mechanophores") in hydrogel networks have become the focus of research interest recently. For instance, typical mechanophores-spiropyran or rhodamine, when covalently incorporated into hydrogel networks constituting of the copolymer of methyl acrylate and acrylamide, could efficiently proceed color change during stretching. [26][27][28][29] The underlying mechanism is based on the opening of the spirocyclic ring to generate the colored and fluorescent isomers. Otsuka et al. demonstrated freezing-induced mechanoluminescence by introducing tetraarylsuccinonitrile moiety as the mechanochromophore at the cross-linking points of a polymer gel. [30][31][32] He et al. found Eu-containing hydrogels showed switchable on/off luminescence along with the force-dependent sol-gel transition through the reversible formation and dissociation of Eu-iminodiacetate complexes. [33] Despite these progresses, most reported mechano-responsive hydrogels displayed color-changing or emission in the visible wavelength region. Very recently, a near-infrared (NIR) mechanophore based on benzo[1,3]oxazine fused with a heptamethine cyanine moiety was developed. Its reversibility exhibited a strong polarity dependence. In polar solvent, irreversible mechanochemical transition was detected. Mechanophores featuring mechanochromism with high color contrast and penetrated NIR emission, as well as reversible mechanochemical switching in the aqueous environment are essential to fabricate NIR mechanochromic hydrogels for force mapping and in situ mechanics sensing, yet remains a great challenge. [34] Mechanofluorochromic polymers, which can indicate damage or excessive stress in highly polarized environments with a clearly perceptible optical signal, are potentially useful in a variety of exciting applications. However, most reported fluorochromic mechanophores exhibit poor color contrast and fluorescence penetration, or are irreversible in polarized phase after mechanical activation. Here, this challenge is tackled by designing and engineering a novel near-infrared (NIR) emissive, rhodanmin derived mechanophore (Rh-Co) in a kin...