Safe confinement of fission iodine isotopes for long-term radioactive waste disposal remains a formidable challenge,as conventional sorbents provide inherently weak iodine-host interactions.We report here a novel halo...Safe confinement of fission iodine isotopes for long-term radioactive waste disposal remains a formidable challenge,as conventional sorbents provide inherently weak iodine-host interactions.We report here a novel halogen bond(X-bond)directed strategy to sequester volatile iodine in hydrogen-bonded(H-bonded)frameworks with unprecedented stability.Charge-assisted Hbonded frameworks bearing open halide sites are developed,showing distinctive iodine encapsulation behaviors without compromising the crystallinity.Direct crystallographic evidence indicates the formation of X-bonds,i.e.,I–I···Cl^(−) and I–I···Br^(−),within the confined pore channels.Unusual polyhalogen anions,i.e.,[I_(2)Cl_(2)]^(2−)and[I_(2)Br_(2)]^(2−),sustained in H-bonded frameworks are identified for the first time.The X-bond reinforced host-guest interaction affords robust iodine trapping without leaking out even at elevated temperatures up to 180℃.By integrating the halogen-bond chemistry with H-bonded frameworks,this study offers fresh concepts for developing effective host reservoirs to secure fission iodine isotopes from spent fuel reprocessing off-gases.展开更多
The development of preparation methods for XOFs,as a new class of organic frameworks,plays a crucial role in shaping their structures,functions,and potential applications.In this study,we presented the construction of...The development of preparation methods for XOFs,as a new class of organic frameworks,plays a crucial role in shaping their structures,functions,and potential applications.In this study,we presented the construction of chiral supramolecular 2D halogen-bonded organic frameworks(XOFs)through a post-synthetic modification strategy.A linear halogen-bonded organic polymer(XOP),XOP-DPBA,decorated with aldehyde groups,was initially prepared to validate the feasibility of post-synthetic modification for XOF construction and functionalization.XOP-DPBA exhibited excellent reactivity with amines,forming imine bonds.By utilizing this reactivity,a series of cross-linked 2D XOFs were efficiently prepared through post-synthetic modified cross-linking reactions.Furthermore,we successfully introduced chiralα/β-cyclodextrins(α/β-CD)into the XOF skeletons via host-guest interactions,resulting in the fabrication of chiral supramolecular 2D XOFs.These chiral XOFs displayed the induced circular dichroism(ICD)signals and assembled them into helical fibers.The post-synthetic modification strategy demonstrated its versatility and simplicity for the construction and functionalization of XOFs.展开更多
The interactions of HF, H2O and NH3 with Br2 are investigated at the MP2（full）/ aug-cc-pVDZ level. It is found that two kinds of stable complexes, halogen-bonded and hydrogen-bonded complexes, exist between Br2 and ...The interactions of HF, H2O and NH3 with Br2 are investigated at the MP2（full）/ aug-cc-pVDZ level. It is found that two kinds of stable complexes, halogen-bonded and hydrogen-bonded complexes, exist between Br2 and HF and between Br2 and H2O. The interaction energy analysis and natural population analysis （NPA） are conducted to these two kinds of complexes, indicating the halogen-bonded complexes are more stable than the corresponding hydrogen-bonded ones, and the binding energies of the former increase in the order HFH2O for the latter.展开更多
基金supported by the National Natural Science Foundation of China(No.22376117)the Tsinghua University Initiative Scientific Research Program.
文摘Safe confinement of fission iodine isotopes for long-term radioactive waste disposal remains a formidable challenge,as conventional sorbents provide inherently weak iodine-host interactions.We report here a novel halogen bond(X-bond)directed strategy to sequester volatile iodine in hydrogen-bonded(H-bonded)frameworks with unprecedented stability.Charge-assisted Hbonded frameworks bearing open halide sites are developed,showing distinctive iodine encapsulation behaviors without compromising the crystallinity.Direct crystallographic evidence indicates the formation of X-bonds,i.e.,I–I···Cl^(−) and I–I···Br^(−),within the confined pore channels.Unusual polyhalogen anions,i.e.,[I_(2)Cl_(2)]^(2−)and[I_(2)Br_(2)]^(2−),sustained in H-bonded frameworks are identified for the first time.The X-bond reinforced host-guest interaction affords robust iodine trapping without leaking out even at elevated temperatures up to 180℃.By integrating the halogen-bond chemistry with H-bonded frameworks,this study offers fresh concepts for developing effective host reservoirs to secure fission iodine isotopes from spent fuel reprocessing off-gases.
基金supported by the National Natural Science Foundation of China(22371218,21702153,21801194)the Wuhan Science and Technology Bureau(whkxjsj009)+1 种基金the support of the Core Facility of Wuhan Universitythe Large-scale Instrument and Equipment Sharing Foundation of Wuhan University。
文摘The development of preparation methods for XOFs,as a new class of organic frameworks,plays a crucial role in shaping their structures,functions,and potential applications.In this study,we presented the construction of chiral supramolecular 2D halogen-bonded organic frameworks(XOFs)through a post-synthetic modification strategy.A linear halogen-bonded organic polymer(XOP),XOP-DPBA,decorated with aldehyde groups,was initially prepared to validate the feasibility of post-synthetic modification for XOF construction and functionalization.XOP-DPBA exhibited excellent reactivity with amines,forming imine bonds.By utilizing this reactivity,a series of cross-linked 2D XOFs were efficiently prepared through post-synthetic modified cross-linking reactions.Furthermore,we successfully introduced chiralα/β-cyclodextrins(α/β-CD)into the XOF skeletons via host-guest interactions,resulting in the fabrication of chiral supramolecular 2D XOFs.These chiral XOFs displayed the induced circular dichroism(ICD)signals and assembled them into helical fibers.The post-synthetic modification strategy demonstrated its versatility and simplicity for the construction and functionalization of XOFs.
基金Supported by the Natural Science Foundation of Zhaoqing University (No. 0523)the Natural Science Foundation of Guangdong Province (No. 5300563)
文摘The interactions of HF, H2O and NH3 with Br2 are investigated at the MP2（full）/ aug-cc-pVDZ level. It is found that two kinds of stable complexes, halogen-bonded and hydrogen-bonded complexes, exist between Br2 and HF and between Br2 and H2O. The interaction energy analysis and natural population analysis （NPA） are conducted to these two kinds of complexes, indicating the halogen-bonded complexes are more stable than the corresponding hydrogen-bonded ones, and the binding energies of the former increase in the order HFH2O for the latter.
