Multifunctionalized epoxy resin (EP) composites are essential for advancing technological innovation across various applications. One efficient method to achieve this is through the development of multifunctional EP fillers. In this work, 2,4,6-tri(pyridin-4-yl)pyridine (Tripp) as electron acceptor and phosphoric acid as electron donor are self-assembled to form a donor–acceptor (D-A) type hydrogen-bonded organic framework (HOF, named P-HOF) using a solvent volatilization method. P-HOF exhibits excellent photochromic and photothermal properties under 365 nm UV irradiation. Electron paramagnetic resonance (EPR) analysis confirms the generation of viologen radicals, and the internal electron transfer mechanism of P-HOF is further elucidated using X-ray photoelectron spectroscopy (XPS). Furthermore, incorporating 3 wt% P-HOF into EP as a filler results in an EP/P-HOF composite that not only retains excellent photochromic and photothermal properties but also demonstrates rapid de-icing and outstanding flame retardancy. The EP/P-HOF coating demonstrates a de-icing efficiency that is 3.83 times higher than that of pure EP coatings. Compared to pure EP, the EP/P-HOF significantly reduced the peak heat release rate (pHRR), total heat release (THR), and peak smoke production rate (pSPR) by 55.0 %, 19.6 %, and 29.6 %, respectively.
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