Due to the fascinating structures and wide applications, porous materials with open frameworks have attracted more and more attentions. Herein, a novel two‐dimensional (2D) halogen‐bonded organic framework (XOF–TPPE) was successfully designed and fabricated by iodonium‐bridged N⋅⋅⋅I+⋅⋅⋅N interactions between pyridyl groups and I+ for the first time. The formation of XOF–TPPE and its linear analogue was monitored by 1H NMR, UV–Vis, X‐ray photoelectron spectroscopy (XPS), IR, SEM, TEM, HRTEM and selected‐area electron diffraction (SAED). The structural model of XOF–TPPE was established based on powder X‐ray diffraction (PXRD) data and theoretical simulations. Significantly, synchrotron small‐angle X‐ray scattering (SAXS), DLS and UV–Vis spectroscopy experiments suggested that XOF–TPPE still maintains a stable 2D framework structure in solutions. This research opens up a novel avenue for the development of organic frameworks materials, and may bring new promising applications for the field of porous materials.

Due to the fascinating structures and wide applications, porous materials with open frameworks have attracted more and more attentions. Herein, a novel two‐dimensional (2D) halogen‐bonded organic framework (XOF–TPPE) was successfully designed and fabricated by iodonium‐bridged N⋅⋅⋅I+⋅⋅⋅N interactions between pyridyl groups and I+ for the first time. The formation of XOF–TPPE and its linear analogue was monitored by 1H NMR, UV–Vis, X‐ray photoelectron spectroscopy (XPS), IR, SEM, TEM, HRTEM and selected‐area electron diffraction (SAED). The structural model of XOF–TPPE was established based on powder X‐ray diffraction (PXRD) data and theoretical simulations. Significantly, synchrotron small‐angle X‐ray scattering (SAXS), DLS and UV–Vis spectroscopy experiments suggested that XOF–TPPE still maintains a stable 2D framework structure in solutions. This research opens up a novel avenue for the development of organic frameworks materials, and may bring new promising applications for the field of porous materials.

The size is an important factor for vesicles, which is essential for their application, especially in nanomedicine and nanomaterials. Unlike polymer vesicles, whose sizes can be controlled by the hydrophobic/hydrophilic...