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Photochromic hexaarylbiimidazoles (HABIs) enable reversible transformation between HABI and triphenylimidazole radicals (TPIRs) upon UV light irradiation, which have been applied in photo-patterning, super-resolution imaging, photoinduced self-healing materials and photomechanical hydrogels. Here, we designed and prepared a novel kind of polyurethane (PU) photoresist based on photo-cleavable HABI cross-linkers (HABI-PU), linear PU backbone and additive tert-butylhydroquinone (TBHQ) radical quencher. Upon UV light irradiation, the C-N bond inside HABI unit is broken, causing the transformation of HABI into two TPIRs which are subsequently quenched by TBHQ. Therefore, the cross-linking points of HABI-PU in UV irradiation area were broken, forming flexible PU polymer chains with declined molecular weight, which can be dissolved in developer. HABI-PU films show excellent photosensitivity as a positive photoresist in photolithography. The reaction mechanism between HABI and TBHQ was studied by UV-vis absorption spectra, electron paramagnetic resonance (EPR), mass spectra and nuclear magnetic resonance spectra. The lithographic patterns were characterized through metallurgical microscope and scanning electron microscope with a resolution at about 5 µm.

Smart materials based on photo-responsive dynamic covalent bonds have the potential for use in many applications, such as photo-modulated manipulators, actuators and self-healing materials. However, the development of high-performance multifunction visible-light-driven dynamic covalent systems has been insufficient. Herein, we report a novel linear polyurethane elastomer (HABI-PU) containing visible-light-switchable hexaarylbiimidazole (HABI) units in the polymer backbone with photo-induced scission and rapid healing capacities. When exposed to 405 nm light, the scratches on the HABI-PU film took only a few seconds to heal. More serious cut damage could be healed after exposure for 30 s and placed in the dark at room temperature for 6 h. Moreover, when a certain weight was loaded during light irradiation, the elastomers broke off as the toughness of the HABI-PU elastomers decreased. The reversible dissociation of the C–N bond of the HABI units caused the scission of long polymer chains into short chains upon light irradiation and further endowed HABI-PU with the properties of photo-induced fracture/healing. Such elastomers are promising for application in the fields of photo-controlled triggers, biomimetic systems, recycled materials, optical machining, and other engineering streams.

Typical cross-linked polymer networks have rubbery elasticity and do not exhibit thermoplasticity such as linear polymers. However, thermodynamically cross-linked polymer networks exhibit certain t...

The magical fantasy of decades-old transformer characters is becoming closer to scientific reality, as transformable materials can change their shapes in response to thermal, mechanical, electrical, and chemical stimuli. However, precise and prompt control of plastic shaping remains to be wanted. Photoresponsive materials provide a promising alternative for rapid optomechanical shaping with limited success. Here, we report a new class of photoplastic transformation based on dynamic covalently crosslinked polytriazole (PTA) networks, in which crosslinking points are comprised of photocleaveable hexaarylbiimidazole (HABI). Upon sub-500 nm light irradiation, HABI is dissociated into two triphenylimidazole radicals (TPIRs) followed by spontaneous recombination back to the initial state. This photoswitching effect is demonstrated to generate nonthermal shape change in the PTA-HABI gel network at will upon light stimulus. A unique photoalignment phenomenon has also been discovered which can form oriented nanoscale patterning in the PTA-HABI gel network upon laser irradiation. The solvent-free PTA-HABI elastomer exhibits photoenhanced automatic self-healing properties at temperatures ranging from 25 °C to freezing points, which is attributed to the dynamic equilibrium between TPIRs and HABI. A photoplastic spring is fabricated and exhibits photoswitchable plastic behavior, i.e., a reversible transformation between plastic strain and elastic strain upon light irradiation. HABI-based polymer networks, including solvated gel and solvent-free elastomer, are promising as smart materials for nonthermal photoactivated shape changing, transformation, and self-healing applications.

Photo-driven hydrogel actuators have attracted tremendous attention due to their underwater photo-mechanical applications, but these critical limitations include reliance on harmful UV light, slow driving speed and limited transformation morphologies need to be further resolved. Here, the transparent polyurethane (PU) hydrogels containing dual networks of dynamic covalent crosslinked hexaarylbiimidazole (HABI) and permanent-crosslinked pentaerythritol units are fabricated and exhibit diversified anisotropic transformations in response to visible light. The underwater three-dimensional (3D) actuations including curling, twisting and folding can be spatiotemporally programmed and achieved within tens of seconds. The biomimetic flower and hydrogel wheel enable rapid photo-driven locomotion. The hydrogel actuators possess great fatigue resistance and reusability. Our work provides new insights to the design of underwater biomimetic intelligent actuators based on photochemically transformation.