The development of organic frameworks with radical skeletons is desired.In this study,we report the development of a novel two-dimensional radical halogen-bonded organic framework(XOF).The radical monomer,benzimidazol...The development of organic frameworks with radical skeletons is desired.In this study,we report the development of a novel two-dimensional radical halogen-bonded organic framework(XOF).The radical monomer,benzimidazole triphenylmethyl(BTTM),was synthesized through the coupling of TTM radicals with benzimidazole.Initially,the benzimidazole units were coordinated with Ag^(+)ions to create a[N···Ag···N]^(+)framework.Subsequently,the addition of iodine led to the in situ replacement of Ag^(+)with I^(+)ions,forming[N···I···N]^(+)linkers and resulting in the creation of the XOF structure.The resulting XOF-HBTTM and XOF-BTTM structures demonstrated good-crystallinity,confirmed by PXRD,HR-TEM,SEAD,and SAXS analyses.EPR measurements confirmed the preservation of radical characteristics within the XOF framework.Furthermore,SQUID measurements indicated that XOF-BTTM exhibits spin moments of S=1/2 at 2 K,with a saturated magnetization strength peaking at 4.10 emu/g,a notable enhancement compared to 1.87 emu/g for the BTTM monomer.This improvement in magnetism is attributed to the extended spin density distribution and the presence of[N···I···N]^(+)interactions,as suggested by DFT calculations.Additionally,the radical XOF-BTTM exhibited significantly enhanced electrical conductivity,reaching up to 1.30×10^(-4)S/cm,which is two orders of magnitude higher than that of XOF-HBTTM.This increased conductivity is linked to a reduced HOMO-LUMO gap,higher carrier density,and the incorporation of triphenylmethyl radicals within the framework.This research highlights the potential of benzimidazolyl motifs in constructing functional XOFs and advances our understanding of radical organic frameworks.展开更多
The escalating utilization of nuclear energy and nuclear medicine raises concerns about the environmental impact of radioactive iodine,necessitating the development of effective iodine adsorbents,especially under a re...The escalating utilization of nuclear energy and nuclear medicine raises concerns about the environmental impact of radioactive iodine,necessitating the development of effective iodine adsorbents,especially under a real-world scenario with extremely low iodine concentration and elevated temperature.Herein,we have presented the construction of a nitrogen-abundant two-dimensional(2D)halogen-bonded organic framework,XOF-TNP,characterized by exceptional crystallinity,thermal stability,and nitrogen-rich structures.XOF-TNP exhibits strong binding to iodine,thanks to the fact that iodine can be pre-enriched into the framework through N…I interactions.The nitrogen-rich framework and I^(+) synergistically have extremely high binding force to iodine,enabling the rapid and efficient capture of iodine in both vapor and solution phases,with significant recyclability.Further flow-through adsorption experiments using an XOF-TNP-packed column achieve 99%iodine removal from hexane and aqueous solutions,surpassing traditional activated carbon.This highlights its potential for environmental remediation.XOFTNP enables the development of a novel rewritable security paper,utilizing its iodine adsorption properties to encrypt and decrypt QR codes.This research expands the application scope of halogen-bonded organic frameworks,providing insights into the design of materials for environmental remediation and security applications.展开更多
Nitrofuran antibiotics threaten human health and the environment due to their toxicity and persistence.Their detection is challenging due to low concentrations and interference,while fluorescence sensing offers superi...Nitrofuran antibiotics threaten human health and the environment due to their toxicity and persistence.Their detection is challenging due to low concentrations and interference,while fluorescence sensing offers superior sensitivity and selectivity for effective monitoring.In this work,a novel halogen-bonded organic framework,XOF-TPEM,was introduced,constructed using an imidazole-based ligand AIE molecule,TPEM.The framework was successfully characterized by various techniques,including 1H NMR,PXRD,XPS,FT-IR,HRTEM,SAED,SEM and EDS,confirming its excellent crystalline structure.As TPEM is an electron-donating AIE fluorophore,the fluorescent XOF-TPEM demonstrates potential as a selective sensor for electron-deficient nitrofuran antibiotics.Experimental results show that it exhibits high sensitivity and selectivity for detecting nitrofurans such as NFT,FZD,FLD,and NFZ,with LODs of 9.7 ppb,11.0 ppb,19.7 ppb,and 236.1 ppb,respectively.Mechanistic studies indicate that the outstanding fluorescence detection performance is attributed to the inner-filter effect occurring between XOF-TPEM and the nitrofuran antibiotics.Through comparison with the sensing performance of a pyridine-based XOF,the superiority of imidazole ligands in constructing XOFs is demonstrated.This study presents a novel luminescent halogen-bonded organic framework and highlights the superiority of imidazole-based halogen-bonded organic frameworks,underscoring their significant potential for expanding their functional applications.展开更多
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-vip 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-vip 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
为了探讨复合物中分子间相互作用对单体分子动力学的影响,对CF3Cl-CO复合物中单体振动谱带基线平移进行了预测。首先,采用二阶多体微扰理论(M?ller-Plesset perturbation theory of second order, MP2)结合扩展相关一致性极化价三重ζ基...为了探讨复合物中分子间相互作用对单体分子动力学的影响,对CF3Cl-CO复合物中单体振动谱带基线平移进行了预测。首先,采用二阶多体微扰理论(M?ller-Plesset perturbation theory of second order, MP2)结合扩展相关一致性极化价三重ζ基组(augmented correlation-consistent polarized valence triple-zeta, Aug-cc-pVTZ)对该复合物的5种结构(S1′、S2、S3、S4、A)进行几何优化、频率计算;然后,引入键函数(3s3p2d1f),在包含单激发、双激发和微扰三激发的耦合簇(coupled cluster with single, double, and perturbative triple excitations, CCSD(T))方法结合Aug-cc-pVTZ的水平上计算稳定结构的分子间相互作用能,并对最稳定结构的单体谱带基线平移进行预测。结果表明,S1′为该复合物的最稳定结构,其分子间相互作用能为-3.81 kJ/mol,其能量分解中交换能占比最高为38%。此外,研究中发现了复合物的2个新的稳定结构S4、A,其分子间相互作用能分别为-2.68、-2.72 kJ/mol。单体谱带基线平移预测表明,在S1′结构中,相比于自由单体振动,复合物中CF3Cl单体的C-Cl键伸缩振动发生了红移,而CO的伸缩振动则表现为蓝移,这表明分子间卤键对分子内动力学存在显著影响。该研究结果为进一步实验测量CF3Cl-CO复合物光谱提供了理论参考。展开更多
基金supported by National Natural Science Foundation of China(Nos.22371218,21702153,52270070 and21801194)Natural Science Foundation of Zhejiang Province(No.LR22B020001)+1 种基金Wuhan Science and Technology Bureau(No.whkxjsj009)the support of the Core Facility of Wuhan University and the Large-scale Instrument and Equipment Sharing Foundation of Wuhan University。
文摘The development of organic frameworks with radical skeletons is desired.In this study,we report the development of a novel two-dimensional radical halogen-bonded organic framework(XOF).The radical monomer,benzimidazole triphenylmethyl(BTTM),was synthesized through the coupling of TTM radicals with benzimidazole.Initially,the benzimidazole units were coordinated with Ag^(+)ions to create a[N···Ag···N]^(+)framework.Subsequently,the addition of iodine led to the in situ replacement of Ag^(+)with I^(+)ions,forming[N···I···N]^(+)linkers and resulting in the creation of the XOF structure.The resulting XOF-HBTTM and XOF-BTTM structures demonstrated good-crystallinity,confirmed by PXRD,HR-TEM,SEAD,and SAXS analyses.EPR measurements confirmed the preservation of radical characteristics within the XOF framework.Furthermore,SQUID measurements indicated that XOF-BTTM exhibits spin moments of S=1/2 at 2 K,with a saturated magnetization strength peaking at 4.10 emu/g,a notable enhancement compared to 1.87 emu/g for the BTTM monomer.This improvement in magnetism is attributed to the extended spin density distribution and the presence of[N···I···N]^(+)interactions,as suggested by DFT calculations.Additionally,the radical XOF-BTTM exhibited significantly enhanced electrical conductivity,reaching up to 1.30×10^(-4)S/cm,which is two orders of magnitude higher than that of XOF-HBTTM.This increased conductivity is linked to a reduced HOMO-LUMO gap,higher carrier density,and the incorporation of triphenylmethyl radicals within the framework.This research highlights the potential of benzimidazolyl motifs in constructing functional XOFs and advances our understanding of radical organic frameworks.
基金supported by the National Natural Science Foundation of China (22371218, 21702153, and 21801194)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 escalating utilization of nuclear energy and nuclear medicine raises concerns about the environmental impact of radioactive iodine,necessitating the development of effective iodine adsorbents,especially under a real-world scenario with extremely low iodine concentration and elevated temperature.Herein,we have presented the construction of a nitrogen-abundant two-dimensional(2D)halogen-bonded organic framework,XOF-TNP,characterized by exceptional crystallinity,thermal stability,and nitrogen-rich structures.XOF-TNP exhibits strong binding to iodine,thanks to the fact that iodine can be pre-enriched into the framework through N…I interactions.The nitrogen-rich framework and I^(+) synergistically have extremely high binding force to iodine,enabling the rapid and efficient capture of iodine in both vapor and solution phases,with significant recyclability.Further flow-through adsorption experiments using an XOF-TNP-packed column achieve 99%iodine removal from hexane and aqueous solutions,surpassing traditional activated carbon.This highlights its potential for environmental remediation.XOFTNP enables the development of a novel rewritable security paper,utilizing its iodine adsorption properties to encrypt and decrypt QR codes.This research expands the application scope of halogen-bonded organic frameworks,providing insights into the design of materials for environmental remediation and security applications.
基金supported by National Natural Science Foundation of China(22371218,21702153,52270070 and 21801194)Wuhan Science and Technology Bureau(whkxjsjoo9)support of the Core Facility of Wuhan University and the Large-scale Instrument and Equipment Sharing Foundation of Wuhan University。
文摘Nitrofuran antibiotics threaten human health and the environment due to their toxicity and persistence.Their detection is challenging due to low concentrations and interference,while fluorescence sensing offers superior sensitivity and selectivity for effective monitoring.In this work,a novel halogen-bonded organic framework,XOF-TPEM,was introduced,constructed using an imidazole-based ligand AIE molecule,TPEM.The framework was successfully characterized by various techniques,including 1H NMR,PXRD,XPS,FT-IR,HRTEM,SAED,SEM and EDS,confirming its excellent crystalline structure.As TPEM is an electron-donating AIE fluorophore,the fluorescent XOF-TPEM demonstrates potential as a selective sensor for electron-deficient nitrofuran antibiotics.Experimental results show that it exhibits high sensitivity and selectivity for detecting nitrofurans such as NFT,FZD,FLD,and NFZ,with LODs of 9.7 ppb,11.0 ppb,19.7 ppb,and 236.1 ppb,respectively.Mechanistic studies indicate that the outstanding fluorescence detection performance is attributed to the inner-filter effect occurring between XOF-TPEM and the nitrofuran antibiotics.Through comparison with the sensing performance of a pyridine-based XOF,the superiority of imidazole ligands in constructing XOFs is demonstrated.This study presents a novel luminescent halogen-bonded organic framework and highlights the superiority of imidazole-based halogen-bonded organic frameworks,underscoring their significant potential for expanding their functional applications.
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-vip 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-vip 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.
文摘为了探讨复合物中分子间相互作用对单体分子动力学的影响,对CF3Cl-CO复合物中单体振动谱带基线平移进行了预测。首先,采用二阶多体微扰理论(M?ller-Plesset perturbation theory of second order, MP2)结合扩展相关一致性极化价三重ζ基组(augmented correlation-consistent polarized valence triple-zeta, Aug-cc-pVTZ)对该复合物的5种结构(S1′、S2、S3、S4、A)进行几何优化、频率计算;然后,引入键函数(3s3p2d1f),在包含单激发、双激发和微扰三激发的耦合簇(coupled cluster with single, double, and perturbative triple excitations, CCSD(T))方法结合Aug-cc-pVTZ的水平上计算稳定结构的分子间相互作用能,并对最稳定结构的单体谱带基线平移进行预测。结果表明,S1′为该复合物的最稳定结构,其分子间相互作用能为-3.81 kJ/mol,其能量分解中交换能占比最高为38%。此外,研究中发现了复合物的2个新的稳定结构S4、A,其分子间相互作用能分别为-2.68、-2.72 kJ/mol。单体谱带基线平移预测表明,在S1′结构中,相比于自由单体振动,复合物中CF3Cl单体的C-Cl键伸缩振动发生了红移,而CO的伸缩振动则表现为蓝移,这表明分子间卤键对分子内动力学存在显著影响。该研究结果为进一步实验测量CF3Cl-CO复合物光谱提供了理论参考。
