A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescenc...A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescence(TADF)properties.All calculations were performed using density functional theory(DFT)and time‑dependent density functional theory(TDDFT).Calculations for electronic structures,frontier molecular orbital characteristics(which determine the efficiency roll‑off effect of the complexes),and photophysical properties were conducted using the Gaussian 09 software package.The calculation of spin‑orbit coupling matrix elements<T|HSOC|S>,which determine the TADF properties of the complexes,was performed using the ORCA software package.The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate(tpip),a strong electron‑withdrawing group,can mitigate the efficiency roll‑off effect of the complex.Furthermore,TADF is observed in one of the designed complexes,(F_(3)Phppy)_(2)Ir(tpip),where F_(3)Phppy=2‑[4‑(2,4,6‑trifluorophenyl)phenyl]pyridine.展开更多
Supramolecular catalysis uses noncovalent interactions,such as hydrogen bonding,π-π stacking,and host-vip recognition,to control reactivity and selectivity in chemical reactions [1,2].Unlike traditional covalent c...Supramolecular catalysis uses noncovalent interactions,such as hydrogen bonding,π-π stacking,and host-vip recognition,to control reactivity and selectivity in chemical reactions [1,2].Unlike traditional covalent catalysis,supramolecular systems can create dynamic and adaptable microenvironments tailored to specific substrates,similar to how enzymes work.This strategy has shown great promise in asymmetric catalysis,cascade reactions,and green chemistry applications.Recent advances focus on leveraging less conventional noncovalent forces to expand the toolbox of supramolecular strategies in catalysis.展开更多
Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments re...Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.展开更多
The emergence of precision electronic devices and wearable electronic products urgently requires high-performance multifunctional electromagnetic wave(EMW)absorbers to meet the applicability and versatility in various...The emergence of precision electronic devices and wearable electronic products urgently requires high-performance multifunctional electromagnetic wave(EMW)absorbers to meet the applicability and versatility in various applications.Herein,a dual-network(DN)gel was successfully prepared using acrylamide and sodium lignosulphonate as the basic units by simple chemical cross-linking and physical cross-linking methods.Specifically,the hydrogel forms two types of cross-linking networks through metal coordination and hydrogen bonding.Benefiting from the combined effects of dipole polarization and conductivity loss,the gel achieves an effective absorption bandwidth(EAB)of 6.74 GHz at a thickness of only 1.89 mm,demonstrating excellent EMW absorption performance.In addition,this unique structural configuration endows the EMW absorber with multifunctional features,such as remarkable tensile strength,good environmental compatibility,ultraviolet(UV)resistance,and excellent adhesion.Integrating multiple functional features into the EMW gels displays a broad application prospect in a variety of application scenarios.This research reveals the significance of DN structure design in the electromagnetic wave absorption(EWA)performance of gel-based materials,providing a substantial foundation for the multifunctional design of gel-based absorbers.展开更多
Interlocked covalent organic cages have aesthetic skeletons endowed with structural and topological complexity.Their self-assembly provides a unique possibility to mimic the hierarchical self-assembly of biomacromolec...Interlocked covalent organic cages have aesthetic skeletons endowed with structural and topological complexity.Their self-assembly provides a unique possibility to mimic the hierarchical self-assembly of biomacromolecules.In recent years,significant progresses in interlocked covalent organic cages have been witnessed.Different topological structures have been fabricated via various non-template induced methods,and diverse weak interactions are demonstrated to play critical roles in guiding the formation of interlocked structures.Therefore,this article systematically summarizes the recent advances in interlocked covalent organic cages,especially their design,synthesis,and self-assembly properties.Depending on different types of chemical reactions,irreversible and reversible reactions are separately introduced.In each section,proper monomer selection,critical topology design,key driving forces as well as detailed interlocked mechanisms for the formation of interlocked structures,and their self-assembly behaviors in single crystals are discussed detailedly.Finally,the challenge and future development of interlocked covalent organic cages are briefly prospected.展开更多
Exploring high-performance electrocatalysts for the nitrate reduction reaction(NO_(3)RR)is crucial for environmental nitrate removal and ammonia synthesis.Single-atom collaboration with cluster can provide sufficient ...Exploring high-performance electrocatalysts for the nitrate reduction reaction(NO_(3)RR)is crucial for environmental nitrate removal and ammonia synthesis.Single-atom collaboration with cluster can provide sufficient active sites for catalysts to promote NO_(3)RR,yet the unclear synergistic effect between the two hinders their rational design.Herein,a series of Ir_(3)clusters and metal single atoms co-embedded in graphitic carbon nitride(g-CN)catalysts(Ir_(3)M1)were constructed,and the synergistic effects of Ir_(3)clusters and M1 single atoms on the NO_(3)RR catalytic mechanism and activity were systematically explored using density functional theory(DFT)calculations combined with machine learning.Comprehensive evaluations of structural stability and catalytic activity demonstrate that the synergy between single atoms and clusters effectively balances the adsorption energies of key intermediates,yielding exceptional catalytic performance(the limiting potential of Ir_(3)Ti_(1)can reach−0.22 V).Machine learning models further clarify the synergistic mechanism,where the geometric configurations of clusters serve as critical features for modulating the catalytic activity of single-atom sites,whereas the electronic structures of single atoms directly govern the reactivity of cluster sites.This DFT-machine learning approach provides theoretical guidelines for catalyst design and a predictive framework for efficient NO_(3)RR electrocatalysts.展开更多
Traditional strategies for designing hyperhalogens,superatoms with exceptional electron-withdrawing capacity,rely on complex superhalogen assembly,posing significant experimental challenges.Here,we introduce a non-inv...Traditional strategies for designing hyperhalogens,superatoms with exceptional electron-withdrawing capacity,rely on complex superhalogen assembly,posing significant experimental challenges.Here,we introduce a non-invasive dual external field(DEF) approach combining solvent effects and an oriented external electric field(OEEF) to construct hyperhalogens,as demonstrated by density functional theory(DFT) calculations.Our DEF strategy proves versatile,successfully designing hyperhalogens not only in simplified Ag_n^(-) model systems but also in the experimentally synthesized Ag_(25) nanocluster.Using the 3D Ag_(19)^(-) structure as a model,we further reveal the DEF's pivotal role in O_(2) activation,where solvent-OEEF synergy induces tunable O-O bond elongation and charge transfer,proportional to field strength.Our findings establish a field-driven paradigm for hyperhalogen design that preserves native cluster composition,providing a theoretical foundation for tailoring high-performance catalysts through precise activesite modulation.展开更多
Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials.Herein,we report ph...Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials.Herein,we report photo-responsive reversible multicolor supramolecular hydrogel with near-infrared emission,which is constructed by cucurbit[7]uril(CB[7]),cyanostilbene derivative(DAC)and Laponite XLG(LP)via supramolecular cascade assembly.Compared with the free vip molecule DAC,the confinement of macrocycle CB[7]achieve effective near-infrared fluorescence in the aqueous phase from scratch,and the subsequent cascade assembly with LP further restrict the molecular rotation of the DAC,which not only result in a substantial enhancement of the fluorescence intensity,but is also endowed with light-controlled fluorescence on/off both in the solution and hydrogel states.Further,8-hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt(HPTS)is introduced in the cascade assembly to fabricated photocontrollable reversible multicolor luminescence supramolecular hydrogel between red and green induced by Förster resonance energy transfer,which is successfully employed in reversible multiple information encryption.展开更多
文摘A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescence(TADF)properties.All calculations were performed using density functional theory(DFT)and time‑dependent density functional theory(TDDFT).Calculations for electronic structures,frontier molecular orbital characteristics(which determine the efficiency roll‑off effect of the complexes),and photophysical properties were conducted using the Gaussian 09 software package.The calculation of spin‑orbit coupling matrix elements<T|HSOC|S>,which determine the TADF properties of the complexes,was performed using the ORCA software package.The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate(tpip),a strong electron‑withdrawing group,can mitigate the efficiency roll‑off effect of the complex.Furthermore,TADF is observed in one of the designed complexes,(F_(3)Phppy)_(2)Ir(tpip),where F_(3)Phppy=2‑[4‑(2,4,6‑trifluorophenyl)phenyl]pyridine.
文摘Supramolecular catalysis uses noncovalent interactions,such as hydrogen bonding,π-π stacking,and host-vip recognition,to control reactivity and selectivity in chemical reactions [1,2].Unlike traditional covalent catalysis,supramolecular systems can create dynamic and adaptable microenvironments tailored to specific substrates,similar to how enzymes work.This strategy has shown great promise in asymmetric catalysis,cascade reactions,and green chemistry applications.Recent advances focus on leveraging less conventional noncovalent forces to expand the toolbox of supramolecular strategies in catalysis.
基金the National Natural Science Foundation of China(No.21921003 for Z.T.L.and 22201293 for S.B.Y.)Shanghai Sailing Program(No.22YF1458300 for S.B.Y.)for financial support。
文摘Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.
基金supported by the National Natural Science Foundation of China(Nos.52231007,51872238,52074227,and 21806129)the Fundamental Research Funds for the Central Universities(Nos.3102018zy045,3102019AX11,and 5000220455)the Natural Science Basic Research Plan in Shaanxi Province of China(Nos.2017JQ5116 and 2020JM-118).
文摘The emergence of precision electronic devices and wearable electronic products urgently requires high-performance multifunctional electromagnetic wave(EMW)absorbers to meet the applicability and versatility in various applications.Herein,a dual-network(DN)gel was successfully prepared using acrylamide and sodium lignosulphonate as the basic units by simple chemical cross-linking and physical cross-linking methods.Specifically,the hydrogel forms two types of cross-linking networks through metal coordination and hydrogen bonding.Benefiting from the combined effects of dipole polarization and conductivity loss,the gel achieves an effective absorption bandwidth(EAB)of 6.74 GHz at a thickness of only 1.89 mm,demonstrating excellent EMW absorption performance.In addition,this unique structural configuration endows the EMW absorber with multifunctional features,such as remarkable tensile strength,good environmental compatibility,ultraviolet(UV)resistance,and excellent adhesion.Integrating multiple functional features into the EMW gels displays a broad application prospect in a variety of application scenarios.This research reveals the significance of DN structure design in the electromagnetic wave absorption(EWA)performance of gel-based materials,providing a substantial foundation for the multifunctional design of gel-based absorbers.
基金supported by the Science and Technology Research Program of Chongqing Municipal Education Commission (No.KJQN202400807)Natural Science Foundation of Shanghai (No.23ZR1419600)。
文摘Interlocked covalent organic cages have aesthetic skeletons endowed with structural and topological complexity.Their self-assembly provides a unique possibility to mimic the hierarchical self-assembly of biomacromolecules.In recent years,significant progresses in interlocked covalent organic cages have been witnessed.Different topological structures have been fabricated via various non-template induced methods,and diverse weak interactions are demonstrated to play critical roles in guiding the formation of interlocked structures.Therefore,this article systematically summarizes the recent advances in interlocked covalent organic cages,especially their design,synthesis,and self-assembly properties.Depending on different types of chemical reactions,irreversible and reversible reactions are separately introduced.In each section,proper monomer selection,critical topology design,key driving forces as well as detailed interlocked mechanisms for the formation of interlocked structures,and their self-assembly behaviors in single crystals are discussed detailedly.Finally,the challenge and future development of interlocked covalent organic cages are briefly prospected.
基金the financial support from the Shandong Province colleges and universities youth innovation technology plan innovation team project(2022KJ285)the Natural Science Foundation of Shandong Province(ZR2022QE076)+1 种基金the National Natural Science Foundation of China(52202092)the Science and Technology Support Plan for Youth Innovation of Colleges and Universities of Shandong Province of China(2023KJ104).
文摘Exploring high-performance electrocatalysts for the nitrate reduction reaction(NO_(3)RR)is crucial for environmental nitrate removal and ammonia synthesis.Single-atom collaboration with cluster can provide sufficient active sites for catalysts to promote NO_(3)RR,yet the unclear synergistic effect between the two hinders their rational design.Herein,a series of Ir_(3)clusters and metal single atoms co-embedded in graphitic carbon nitride(g-CN)catalysts(Ir_(3)M1)were constructed,and the synergistic effects of Ir_(3)clusters and M1 single atoms on the NO_(3)RR catalytic mechanism and activity were systematically explored using density functional theory(DFT)calculations combined with machine learning.Comprehensive evaluations of structural stability and catalytic activity demonstrate that the synergy between single atoms and clusters effectively balances the adsorption energies of key intermediates,yielding exceptional catalytic performance(the limiting potential of Ir_(3)Ti_(1)can reach−0.22 V).Machine learning models further clarify the synergistic mechanism,where the geometric configurations of clusters serve as critical features for modulating the catalytic activity of single-atom sites,whereas the electronic structures of single atoms directly govern the reactivity of cluster sites.This DFT-machine learning approach provides theoretical guidelines for catalyst design and a predictive framework for efficient NO_(3)RR electrocatalysts.
基金supported by the National Natural Science Foundation of China (NSFC,Nos.12474274,92161101)the Innovation Project of Jinan Science and Technology Bureau(No.2021GXRC032)the Natural Science Foundation of Shandong Province (No.ZR2024MA091)。
文摘Traditional strategies for designing hyperhalogens,superatoms with exceptional electron-withdrawing capacity,rely on complex superhalogen assembly,posing significant experimental challenges.Here,we introduce a non-invasive dual external field(DEF) approach combining solvent effects and an oriented external electric field(OEEF) to construct hyperhalogens,as demonstrated by density functional theory(DFT) calculations.Our DEF strategy proves versatile,successfully designing hyperhalogens not only in simplified Ag_n^(-) model systems but also in the experimentally synthesized Ag_(25) nanocluster.Using the 3D Ag_(19)^(-) structure as a model,we further reveal the DEF's pivotal role in O_(2) activation,where solvent-OEEF synergy induces tunable O-O bond elongation and charge transfer,proportional to field strength.Our findings establish a field-driven paradigm for hyperhalogen design that preserves native cluster composition,providing a theoretical foundation for tailoring high-performance catalysts through precise activesite modulation.
基金National Natural Science Foundation of China (NSFC) (No.22131008)the Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials.Herein,we report photo-responsive reversible multicolor supramolecular hydrogel with near-infrared emission,which is constructed by cucurbit[7]uril(CB[7]),cyanostilbene derivative(DAC)and Laponite XLG(LP)via supramolecular cascade assembly.Compared with the free vip molecule DAC,the confinement of macrocycle CB[7]achieve effective near-infrared fluorescence in the aqueous phase from scratch,and the subsequent cascade assembly with LP further restrict the molecular rotation of the DAC,which not only result in a substantial enhancement of the fluorescence intensity,but is also endowed with light-controlled fluorescence on/off both in the solution and hydrogel states.Further,8-hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt(HPTS)is introduced in the cascade assembly to fabricated photocontrollable reversible multicolor luminescence supramolecular hydrogel between red and green induced by Förster resonance energy transfer,which is successfully employed in reversible multiple information encryption.
