4.7 Article

Self-healing, tough, red-to-near-infrared (NIR) luminescent organohydrogels derived from supramolecular assemblies of common aggregation-induced emissive luminogens

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CHEMICAL ENGINEERING JOURNAL
卷 463, 期 -, 页码 -

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ELSEVIER SCIENCE SA
DOI: 10.1016/j.cej.2023.142307

关键词

Polymeric gel; Aggregation-induced emission; Supramolecular assembly; Red-to-NIR luminescence; Organohydrogel

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In this study, red-to-NIR luminescent polymeric gels based on supramolecular co-assemblies of cationic terpyridine platinum (II) luminogen and anionic alginate were reported. The large red-shifted emission and good preservation of luminescence after incorporation into crosslinked poly(vinyl alcohol) networks were observed. These organohydrogels exhibited high stress-bearing capacity, pH-responsive emission, self-healing and remolding abilities, as well as biocompatibility.
Luminescent polymeric gels (LPGs) are promising for wide high-tech applications due to their hydrated state, tunable emission and similarity to bio-tissues. However, most LPGs only exhibit visible luminescence below 630 nm and cannot emit the preferred near-infrared (NIR) luminescence (650 -900 nm). Herein, we report red-to-NIR aggregation-induced emissive LPGs based on supramolecular co-assemblies of cationic terpyridine platinum (II) luminogen (TPY-Pt) and anionic alginate (Alg) with unexpected large red emission shift (-100 nm). Com-bined analyses of UV-Vis/emission spectra, transmission electron microscopy (TEM), dynamic light scattering (DLS), zeta potential results, and density functional theory (DFT) calculations suggested that such large red-shifted emission derived from coupling of the dyes' transition dipole moments in TPY-Pt/Alg co-assemblies. Interestingly, red-to-NIR luminescence was well-preserved after TPY-Pt/Alg co-assemblies were physically incorporated into crosslinked poly(vinyl alcohol) (PVA) networks. Consequently, PVA organohydrogels and hydrogels with red-to-NIR emission bands respectively centered at 698 nm and 708 nm were obtained. After further mechanical training to induce anisotropic orientational structures, these PVA organohydrogels were able to bear a high stress of 1.4 MPa. They also had pH-responsive emission, self-healing and remolding capacities, and biocompatibility. The developed red-to-NIR luminescent organohydrogels with these integrated merits have been seldom reported and are expected to find many potential applications.

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