Organic donor-acceptor cocrystals ofπ-conjugated molecues have shown diverse applications in materials science.However,most cocrystals exist in neutral forms dominated byπ-πinteractions,while the ionic congeners an...Organic donor-acceptor cocrystals ofπ-conjugated molecues have shown diverse applications in materials science.However,most cocrystals exist in neutral forms dominated byπ-πinteractions,while the ionic congeners and corresponding properties are rarely studied due to difficulties in harnessing the degree of charge transfer.Herein,we report cocrystals of axially N-embedded quasi-carbon nanohoops(DPP-D and DPP-T)with electron deficient vips.By modulating the electron affinity of the acceptor vips,the electronic structures of the complexes can be tuned from neutral to ionic states.Specifically,DPP-D interacts with TCNB molecules to form neutral superstructures via intermolecularπ-πinteractions,giving rise to a deep-red emission in the solid state.In contrast,an ionic complex showing near-infrared region absorptions and paramagnetic character on account of strong charge-transfer interactions is generated when DDQ molecules are involved.Their unique properties can be explained by different degrees of charge transfer and assembly modes,which have clearly been manifested by crystal structures and theoretical calculations.Our studies provide rare examples ofπ-conjugated macrocycle-based donor-acceptor cocrystals in both neutral and ionic forms,and give insight to the design of multicomponent carbon nanomaterials.展开更多
Carbon nanohoop,a class of constrained molecular architecture consisting of linked arene units,has attracted considerable interest from both experimental and theoretical chemists due to its synthetic challenge and aes...Carbon nanohoop,a class of constrained molecular architecture consisting of linked arene units,has attracted considerable interest from both experimental and theoretical chemists due to its synthetic challenge and aesthetic architectures.Another fascinating and synthetically challenging species,the Mobius-type molecule,has been attracting the scientific community with its elegant structure and aromaticity.Thus,combining two things together,synthesizing a carbon nanohoop with Mobius topology remains more challenging to date.Here we report a cyclophenylene featuring Mobius strip characterized by X-ray crystallography.Theoretical calculations reveal that such type of nanohoop is fully conjugated systems with electrons delocalized both inπsextets and the bridging carbon–carbon bonds.This work highlights that the manipulation of phenylene connection in a carbon nanohoop can help obtain more delicate and aesthetic molecular architectures.展开更多
Spin-based interdisciplinary research has attracted considerable attention,and various applications in magnetic memory,quantum science,and precision measuring technology have been reported.In this study,we induced a f...Spin-based interdisciplinary research has attracted considerable attention,and various applications in magnetic memory,quantum science,and precision measuring technology have been reported.In this study,we induced a fluorescence property in a spin-active molecule by supramolecular assembly and realized a synergistic modulation of its spin and fluorescence properties.A Saturn-shaped supramolecular complex was synthesized using a spin-active metallofullerene Sc_(3)C_(2)@C80 with a fluorescent nanohoop of tetra-benzothiadiazole-based[12]cycloparaphenylene(TB[12]CPP),and its spin and fluorescence properties were comprehensively investigated.Temperature-dependent electron paramagnetic resonance(EPR)spectroscopy and fluorescence analyses were conducted.Synchronous changes in the EPR signals and fluorescence peaks were discovered in the temperature range of 170–290 K.Based on nuclear magnetic resonance observations and theoretical calculations,a temperature-dependent host–vip interaction between Sc_(3)C_(2)@C_(80)and a nanohoop was demonstrated,which explained the synchronous changes in the EPR signals and fluorescence peaks for Sc_(3)C_(2)@C_(80)⊂TB[12]CPP.The application of Sc_(3)C_(2)@C_(80)as a molecular spin system to probe the host–vip interaction was also evaluated.These results show that the supramolecular assembly can be used to design advanced spin systems coupled with optical and magnetic behaviors based on paramagnetic and luminescent molecules.展开更多
Curvedπ-electron systems show unique properties and assembly feature that enable the specific applications in materials science and supramolecular chemistry.Herein,fullerene,carbon nanohoop andπ-bowl are integrated ...Curvedπ-electron systems show unique properties and assembly feature that enable the specific applications in materials science and supramolecular chemistry.Herein,fullerene,carbon nanohoop andπ-bowl are integrated by the coupling of covalent and supramolecular tactics.Firstly,π-bowl trichalcogenasumanenes(TCSs)are fused with a carbon nanohoop[10]CPP via covalent joint to form molecular crowns 4a/4b,which show structural and electronic complementarity and accordingly strong binding affinity to C_(60)/C_(70).Secondly,the supramolecular assemblies of 4a/4b with fullerenes afford the host-vip complexes 4a/4b⊃C_(60)/C_(70) in solution(molar ratio,2:1)and solid state(molar ratio,1:1).In the crystals of host–vip complexes,the intra-cluster and inter-cluster interactions are respectively dominated by the[10]CPP and TCSs moieties of 4a/4b.Additionally,it is found that 4a/4b are good photosensitizers for generating ^(1)O_(2) and show structural adaptability in accordance to assembly conditions.4a/4b take an endo-conformation in their own crystals with TCSs and[10]CPP moieties being bowl-shaped and elliptical,respectively.In contrast,the[10]CPP on 4a/4b changes into circular and the TCSs moiety becomes flat(for 4b)or shows bowl inversion to be exo-conformation(for 4a)in 4a/4b⊃C_(60)/C_(70).展开更多
基金supported by the National Natural Science Foundation of China(22025503,22220102004)。
文摘Organic donor-acceptor cocrystals ofπ-conjugated molecues have shown diverse applications in materials science.However,most cocrystals exist in neutral forms dominated byπ-πinteractions,while the ionic congeners and corresponding properties are rarely studied due to difficulties in harnessing the degree of charge transfer.Herein,we report cocrystals of axially N-embedded quasi-carbon nanohoops(DPP-D and DPP-T)with electron deficient vips.By modulating the electron affinity of the acceptor vips,the electronic structures of the complexes can be tuned from neutral to ionic states.Specifically,DPP-D interacts with TCNB molecules to form neutral superstructures via intermolecularπ-πinteractions,giving rise to a deep-red emission in the solid state.In contrast,an ionic complex showing near-infrared region absorptions and paramagnetic character on account of strong charge-transfer interactions is generated when DDQ molecules are involved.Their unique properties can be explained by different degrees of charge transfer and assembly modes,which have clearly been manifested by crystal structures and theoretical calculations.Our studies provide rare examples ofπ-conjugated macrocycle-based donor-acceptor cocrystals in both neutral and ionic forms,and give insight to the design of multicomponent carbon nanomaterials.
基金This work was supported by the National Natural Science Foundation of China(21873079,21771155,92061103,21721001,21573179)the Ministry of Science and Technology of China(2017YFA0204902)+1 种基金the Fundamental Research Funds for the Central Universities(20720180035)the Top-Notch Young Talents Program of China.
文摘Carbon nanohoop,a class of constrained molecular architecture consisting of linked arene units,has attracted considerable interest from both experimental and theoretical chemists due to its synthetic challenge and aesthetic architectures.Another fascinating and synthetically challenging species,the Mobius-type molecule,has been attracting the scientific community with its elegant structure and aromaticity.Thus,combining two things together,synthesizing a carbon nanohoop with Mobius topology remains more challenging to date.Here we report a cyclophenylene featuring Mobius strip characterized by X-ray crystallography.Theoretical calculations reveal that such type of nanohoop is fully conjugated systems with electrons delocalized both inπsextets and the bridging carbon–carbon bonds.This work highlights that the manipulation of phenylene connection in a carbon nanohoop can help obtain more delicate and aesthetic molecular architectures.
基金supported by the National Natural Science Foundation of China(Nos.52022098 and 51972309)the Youth Innovation Promotion Association of Chinese Academy of Sciences(No.Y201910).
文摘Spin-based interdisciplinary research has attracted considerable attention,and various applications in magnetic memory,quantum science,and precision measuring technology have been reported.In this study,we induced a fluorescence property in a spin-active molecule by supramolecular assembly and realized a synergistic modulation of its spin and fluorescence properties.A Saturn-shaped supramolecular complex was synthesized using a spin-active metallofullerene Sc_(3)C_(2)@C80 with a fluorescent nanohoop of tetra-benzothiadiazole-based[12]cycloparaphenylene(TB[12]CPP),and its spin and fluorescence properties were comprehensively investigated.Temperature-dependent electron paramagnetic resonance(EPR)spectroscopy and fluorescence analyses were conducted.Synchronous changes in the EPR signals and fluorescence peaks were discovered in the temperature range of 170–290 K.Based on nuclear magnetic resonance observations and theoretical calculations,a temperature-dependent host–vip interaction between Sc_(3)C_(2)@C_(80)and a nanohoop was demonstrated,which explained the synchronous changes in the EPR signals and fluorescence peaks for Sc_(3)C_(2)@C_(80)⊂TB[12]CPP.The application of Sc_(3)C_(2)@C_(80)as a molecular spin system to probe the host–vip interaction was also evaluated.These results show that the supramolecular assembly can be used to design advanced spin systems coupled with optical and magnetic behaviors based on paramagnetic and luminescent molecules.
基金National Natural Science Foundation of China,Grant/Award Numbers:22371107,22175080the Science and Technology Major Program of Gansu Province of China,Grant/Award Number:22ZD6FA006。
文摘Curvedπ-electron systems show unique properties and assembly feature that enable the specific applications in materials science and supramolecular chemistry.Herein,fullerene,carbon nanohoop andπ-bowl are integrated by the coupling of covalent and supramolecular tactics.Firstly,π-bowl trichalcogenasumanenes(TCSs)are fused with a carbon nanohoop[10]CPP via covalent joint to form molecular crowns 4a/4b,which show structural and electronic complementarity and accordingly strong binding affinity to C_(60)/C_(70).Secondly,the supramolecular assemblies of 4a/4b with fullerenes afford the host-vip complexes 4a/4b⊃C_(60)/C_(70) in solution(molar ratio,2:1)and solid state(molar ratio,1:1).In the crystals of host–vip complexes,the intra-cluster and inter-cluster interactions are respectively dominated by the[10]CPP and TCSs moieties of 4a/4b.Additionally,it is found that 4a/4b are good photosensitizers for generating ^(1)O_(2) and show structural adaptability in accordance to assembly conditions.4a/4b take an endo-conformation in their own crystals with TCSs and[10]CPP moieties being bowl-shaped and elliptical,respectively.In contrast,the[10]CPP on 4a/4b changes into circular and the TCSs moiety becomes flat(for 4b)or shows bowl inversion to be exo-conformation(for 4a)in 4a/4b⊃C_(60)/C_(70).
