Feng Weihao, Li Fen, Jiang Zhenyi, Yue Chaojun, Yin Guangqiang, Zhu Ning, Zhang Kai, Chen Tao, Lu Wei
State Key Laboratory of Advanced Marine Materials, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, 315201, P.R. China.
School of Chemical Sciences, University of Chinese Academy of Sciences, 19A Yuquan Road, Beijing, 100049, P.R. China.
Angew Chem Int Ed Engl. 2025 Jul;64(29):e202505192. doi: 10.1002/anie.202505192. Epub 2025 May 19.
Polymeric room temperature phosphorescence (RTP) hydrogels are emerging candidates for many advanced photonic applications. Unfortunately, phosphorescence of the introduced RTP chromophores can easily be quenched in water-swollen hydrogel networks, limiting their luminescence performance and application adaptability. Herein, we propose a supramolecular confinement-entanglement synergy strategy to produce ultrastretchable RTP hydrogels by in-situ polymerizing high-concentration 2-(acryloyloxy)ethyl trimethylammonium chloride (AETC) in the presence of preassembled 4-biphenylboronic acid@β-cyclodextrin (4-BB@β-CD) emissive aggregates. The hyper-entangled poly(AETC) (PAETC) chains, formed under water-limiting conditions, synergistically densify the 4-BB@β-CD aggregates through supramolecular confinement, effectively suppressing molecular vibrations and stabilizing triplet states. Impressively, the hydrogels exhibit intense afterglow and ultralong phosphorescence lifetime up to 1.1 s under room conditions. Crucially, the entanglement-dominated physical network free of static chemical crosslinking enables continuing chain disentanglement during stretching for efficient energy dissipation. Segment length between physical entanglement points can thus be significantly enlarged to reduce network fracture and avoid crack propagation, achieving record-breaking uniaxial/biaxial (21 000%/10 000%) stretchability. Even the notched hydrogels are capable of being unprecedentedly stretched to 20 500% and exhibit a fracture energy as high as 157 kJ m⁻, demonstrating intrinsic crack-tolerance. This study opens new avenues of polymeric RTP hydrogels by bringing superior mechanical performance and should merit their application exploration.
聚合物室温磷光（RTP）水凝胶正成为许多先进光子应用的候选材料。不幸的是，引入的RTP发色团在水溶胀水凝胶网络中很容易被猝灭，这限制了它们的发光性能和应用适应性。在此，我们提出一种超分子限域 - 缠结协同策略，通过在预组装的4 - 联苯硼酸@β - 环糊精（4 - BB@β - CD）发光聚集体存在下原位聚合高浓度的2 - （丙烯酰氧基）乙基三甲基氯化铵（AETC）来制备超拉伸性RTP水凝胶。在限水条件下形成的超缠结聚（AETC）（PAETC）链通过超分子限域协同致密化4 - BB@β - CD聚集体，有效抑制分子振动并稳定三重态。令人印象深刻的是，该水凝胶在室温条件下表现出强烈的余辉和长达1.1秒的超长磷光寿命。至关重要的是，以缠结为主的物理网络不含静态化学交联，使得在拉伸过程中链能够持续解缠结以实现高效的能量耗散。因此，物理缠结点之间的链段长度可以显著增大，以减少网络断裂并避免裂纹扩展，实现创纪录的单轴/双轴（21000%/10000%）拉伸性。即使是带缺口的水凝胶也能够被前所未有的拉伸至20500%，并表现出高达157 kJ m⁻²的断裂能，证明了其内在的抗裂性。这项研究通过赋予聚合物RTP水凝胶优异的机械性能开辟了新途径，值得对其进行应用探索。
