A Type of Halogen-Bonded Organic Frameworks Based on N⋯Cl ⁺ ⋯N Bonds: Stabilizing Sensitive Species

It remains a significant challenge to explore halogen bonds based on chlorine, despite extensive investigation into those involving larger halogen atoms like iodine and bromine.[N Cl N] + halogen bond was usually unstable and typically only obtainable at extremely low temperatures (approximately -80 C) due to chlorine's high electronegativity.In this work, we demonstrated the inaugural construction of stable chlorine(I)-bridged two-dimensional (2D) halogen-bonded organic frameworks (XOFs) utilizing sensitive [N Cl N] + halogen bonds.The formation of XOF(Cl)-TPy-BF 4 /OTf was investigated using 1 H NMR, XPS, IR, HR-TEM, and SEAD, PXRD, SAXS, exhibiting their good crystallinity.Unlike the highly unstable Py 2 ClBF 4 , XOF(Cl) displayed remarkable chemical and thermal stability, even maintaining the periodic framework integrity across various organic solvents.Moreover, the XOF(Cl) can be utilized as a platform to stabilize and immobilize the reactive Pd(0) clusters among the frameworks.The resulting XOF(Cl)-TPy-Pd 0 demonstrated excellent catalytic activities in various Pd-catalyzed coupling reactions, including Suzuki, Heck, and Sonogashira couplings, affording high yields even Page 1 of 52 CCS Chemistry