A series of perylenetetracarboxylic diimides (PDIs) dimers with slipped “face-to-face” stacked structure and different substituents at the bay positions have been synthesized and the molecular structures are charact...A series of perylenetetracarboxylic diimides (PDIs) dimers with slipped “face-to-face” stacked structure and different substituents at the bay positions have been synthesized and the molecular structures are characterized by 1H NMR, MALDI-TOF and elemental analysis. And different substituents at the bay positions of the PDI ring bring about various steric hindrances. These different steric hindrances have caused significant differences on the absorption and emission spectra. The correlation between the photophysical properties and the molecular structure is discussed.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 new ligand of N-benzyl-N＇-（2-pyridyl）urea L and its self-assembly product with CuCl2, [Cu（Ⅱ）LCl2]∞ 1, have been synthesized and structurally characterized by IR, 1H NMR and single-crystal X-ray diffraction an...A new ligand of N-benzyl-N＇-（2-pyridyl）urea L and its self-assembly product with CuCl2, [Cu（Ⅱ）LCl2]∞ 1, have been synthesized and structurally characterized by IR, 1H NMR and single-crystal X-ray diffraction analysis. In the structure of L, the urea groups adopt Z,E conformation to form dimers through intermolecular hydrogen bonds; while in complex 1, it assumes Z,Z conformation to fit for the coordination sphere of the Cu（Ⅱ） ions. The coordinated units are connected through intermolecular N-H...Cl hydrogen bonds to form an extended 2D framework. Finally, a 3D structure is obtained via π-π stacking interactions between pyridyl rings展开更多
文摘A series of perylenetetracarboxylic diimides (PDIs) dimers with slipped “face-to-face” stacked structure and different substituents at the bay positions have been synthesized and the molecular structures are characterized by 1H NMR, MALDI-TOF and elemental analysis. And different substituents at the bay positions of the PDI ring bring about various steric hindrances. These different steric hindrances have caused significant differences on the absorption and emission spectra. The correlation between the photophysical properties and the molecular structure is discussed.
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.
文摘A new ligand of N-benzyl-N＇-（2-pyridyl）urea L and its self-assembly product with CuCl2, [Cu（Ⅱ）LCl2]∞ 1, have been synthesized and structurally characterized by IR, 1H NMR and single-crystal X-ray diffraction analysis. In the structure of L, the urea groups adopt Z,E conformation to form dimers through intermolecular hydrogen bonds; while in complex 1, it assumes Z,Z conformation to fit for the coordination sphere of the Cu（Ⅱ） ions. The coordinated units are connected through intermolecular N-H...Cl hydrogen bonds to form an extended 2D framework. Finally, a 3D structure is obtained via π-π stacking interactions between pyridyl rings
