Herein,we report an efficient one-pot condensation of maleimide derivatives in the presence of acetic acid and water to afford a series of benzene triimides (BTIs).The structure,physicochemical properties and electroc...Herein,we report an efficient one-pot condensation of maleimide derivatives in the presence of acetic acid and water to afford a series of benzene triimides (BTIs).The structure,physicochemical properties and electrochemistry behavior of BTIs were studied by means of X-ray crystallography,UV-Vis spectra,cyclic voltammetry and differential pulse voltammetry.Owing to the planar structure and unique electron-deficient nature,BTIs can self-assemble into different motifs including nanorod,nanotube,nanobrick and cross-linked structure depending on different N-substituents.The origin for different self-assemblies was ascribed to the intermolecular lone pair-π interaction or a balance of lone pair-π and π-π stacking.展开更多
We herein present the efficient syntheses,crystal structures,and physical properties of a series of novel benzene triimide(BTI)radical anions,emphasizing the relationship between molecular structure with spin–spin in...We herein present the efficient syntheses,crystal structures,and physical properties of a series of novel benzene triimide(BTI)radical anions,emphasizing the relationship between molecular structure with spin–spin intermolecular interactions and physical properties in the crystalline state.BTI radical crystals were preparedby reducingvarious substitutedBTIs(1)with cobaltocene(CoCp2),followed by sequential crystallization processes.Two isolable radical species,that is,neutral molecule-radical anion pair(2)and monoradical species(3),were obtained from BTIs bearing small substituents(ethyl and propyl),while for those bearing larger substituents(butyl,hexyl,and benzyl)sole monoradicals(3)were produced.The radical species showed diverse intermolecular stackings in the crystalline state referred to asπ-pimer,π-dimer,alternatingπ-trimer,and one-dimensional(1D)slippedπ-stacks depending on the length and size of the substituents.Different spin–spin interactions arising from the substituent-tuned radical packings were demonstrated by electron spin resonance(ESR)spectra.The structure–property relationshipwas studied in terms of magnetism and conductivity.The radicalπ-pimers andπ-stacks with effective charge transport exhibited paramagnetic property and conductivity feasibly at room temperature,whileπ-dimers andπ-trimers featuring thermally populated spin-triplet stateswere antiferromagnetic and nonconductive due to their strong radical–radical pairing effect.展开更多
A triangular prism cage 2 with benzene triimide(BTI)as the base and 2,7-naphthalene dimethylene as the supporting pillars was designed and synthesized efficiently.The two parallel BTI planes constitute a cavity of 7.5...A triangular prism cage 2 with benzene triimide(BTI)as the base and 2,7-naphthalene dimethylene as the supporting pillars was designed and synthesized efficiently.The two parallel BTI planes constitute a cavity of 7.58Åwhich allows the inclusion of anions of various sizes.展开更多
基金We thank the National Natural Science Foundation of China (Nos. 21772203, 21761132024, 21521002, 21871276)Chi-nese Academy of Sciences (QYZDJ-SSW-SLH02B) for financial sup-port. Q.-Q. W. also thanks the Thousand Young Talents Program for support. We thank Prof. Jieping Zhu from EPFL for helpful dis-cussion on the reaction mechanism.
文摘Herein,we report an efficient one-pot condensation of maleimide derivatives in the presence of acetic acid and water to afford a series of benzene triimides (BTIs).The structure,physicochemical properties and electrochemistry behavior of BTIs were studied by means of X-ray crystallography,UV-Vis spectra,cyclic voltammetry and differential pulse voltammetry.Owing to the planar structure and unique electron-deficient nature,BTIs can self-assemble into different motifs including nanorod,nanotube,nanobrick and cross-linked structure depending on different N-substituents.The origin for different self-assemblies was ascribed to the intermolecular lone pair-π interaction or a balance of lone pair-π and π-π stacking.
基金This research was supported by the National Natural Science Foundation of China(no.91956126)Beijing National Laboratory for Molecular Sciences(BNLMS-CXXM-202002 and BMS Junior Fellow Scholarship)China Postdoctoral Science Foundation(no.2020TQ0326).
文摘We herein present the efficient syntheses,crystal structures,and physical properties of a series of novel benzene triimide(BTI)radical anions,emphasizing the relationship between molecular structure with spin–spin intermolecular interactions and physical properties in the crystalline state.BTI radical crystals were preparedby reducingvarious substitutedBTIs(1)with cobaltocene(CoCp2),followed by sequential crystallization processes.Two isolable radical species,that is,neutral molecule-radical anion pair(2)and monoradical species(3),were obtained from BTIs bearing small substituents(ethyl and propyl),while for those bearing larger substituents(butyl,hexyl,and benzyl)sole monoradicals(3)were produced.The radical species showed diverse intermolecular stackings in the crystalline state referred to asπ-pimer,π-dimer,alternatingπ-trimer,and one-dimensional(1D)slippedπ-stacks depending on the length and size of the substituents.Different spin–spin interactions arising from the substituent-tuned radical packings were demonstrated by electron spin resonance(ESR)spectra.The structure–property relationshipwas studied in terms of magnetism and conductivity.The radicalπ-pimers andπ-stacks with effective charge transport exhibited paramagnetic property and conductivity feasibly at room temperature,whileπ-dimers andπ-trimers featuring thermally populated spin-triplet stateswere antiferromagnetic and nonconductive due to their strong radical–radical pairing effect.
基金supported by National Natural Science Foundation of China(grant nos.21772203,22022112,21871276,and 21521002)and Chinese Academy of Sciences(grant no.QYZDJ-SSW-SLH023).
文摘A triangular prism cage 2 with benzene triimide(BTI)as the base and 2,7-naphthalene dimethylene as the supporting pillars was designed and synthesized efficiently.The two parallel BTI planes constitute a cavity of 7.58Åwhich allows the inclusion of anions of various sizes.
