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 structural diversity and the various applications of organic frameworks have attracted much attention in recent years. Recently, halogen-bonded organic frameworks (XOFs) became a novel member of these materials, thereby facilitating the exploration of the interesting structures as well as functions. Here we present two types of [N···I+···N] connected XOFs (XOF-TPy and XOF-TPEB) with two tridentate ligands as building blocks. XOF-TPy and XOF-TPEB were characterized by 1H NMR, UV–vis, X-ray photoelectron spectroscopy (XPS), IR, SEM, and HR-TEM. Two-dimensional (2D) structural models were established based on powder X-ray diffraction (PXRD) data and theoretical simulations. Further experiment showed that these XOFs were excellent iodinating agents for the substituted arylboronic acids with either the electron-donating or electron-withdrawing groups upon heating without any catalyst. This research not only brings further understanding to the XOFs but also extends the applications of XOFs.

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.