The synthetic routes of monomers M1 and M3 are shown in Scheme S1 and the structures were characterized by¹H NMR, ¹³C NMR, and high-resolution mass spectrometry analyses (Figure S1–S3, S5-S7). M2 could be directly by purchased and ¹H NMR spectra was shown in Figure S4.

In previous work, we had shown that M1 could self-assemble in chloroform to form SPs.^[20] To explore the process for adding small molecule M2 and M3 into theM1 solution (Figure 1a), the corresponding ¹H NMR spectra of the M3 (Figure S8), and a mixture of M2 and M3 (Figure S9) at different time were recorded. As shown in Figure 1b, 0.1 equiv. of M3 were added to 50 mmol M1 . Due to the small amount addition of M3 , SPs were not crosslinked to a high enough degree and therefore formed a network rather than a gel. By comparing the ¹H NMR spectra of the mixed solution at 2 h, 4 h, 8 h, 20 h, it could be determined that the reaction was essentially complete after 8 h. The peak of the aldehyde group of M3 at 10.05 ppm was significantly weakened, but the peak did not disappear completely. This was due to the fact that H₂O was generated from the reaction of amine aldehyde condensation causing the hydrolysis of newly formed imine bond, thus leading to incomplete reaction.^[21] In addition, a new peak appeared in the range of 8.20-8.28 ppm, which also proved that the imine bond were generated through the reaction between the amino groups at the ends of M1 and the aldehyde groups ofM3 .^[22]