The theoretical calculation and spectroscopic experiments indicate a kind of triangular three bonding supramolecular complexes CBr4…X^-…-H-C, which consist of carbon tetrabromide, halide, and protic solvent molecule...The theoretical calculation and spectroscopic experiments indicate a kind of triangular three bonding supramolecular complexes CBr4…X^-…-H-C, which consist of carbon tetrabromide, halide, and protic solvent molecule （referring to dichloromethane, chloroform and acetonitrile）, can be formed in solution. The strength of halogen and hydrogen bonds in the triangular complexes using halide as common acceptor obeys the order of iodide〉bromide〉chloride. The halogen and hydrogen bonds work weak-cooperatively. Charge transfer bands of halogen bonding complexes between CBra and halide are observed in UV-Vis absorption spectroscopy in three solvents, and then the stoichiometry of 1：1, formation constants K and molar extinction coefficients ε of the halogen bonding complexes are obtained by Benesi-Hildebrand method. The K and ε show a dependence on the solvent dielectric constant and, on the whole, obey an order of iodide〉bromide〉chloride in the same solvents. Furthermore, the C-H vibrational frequencies of solvent molecules vary obviously with the addition of halide, which indicates the C-H…X- interaction. The experimental data indicate that the halogen bond and hydrogen bond coexist by sharing a common halide acceptor as predicted by calculation.展开更多
Four achiral Cu(Ⅱ)-coordinated Schiff bases complexes containing aromatic structures were synthesized and their supramolecular assemblies at the air/water interface were investigated.All the compounds could be spread...Four achiral Cu(Ⅱ)-coordinated Schiff bases complexes containing aromatic structures were synthesized and their supramolecular assemblies at the air/water interface were investigated.All the compounds could be spread on water surface although they have no alkyl chains.The Schiff base complex molecules with naphthyl groups tended to form J-aggregate in the Langmuir-Blodgett(LB) films transferred from water surface.By investigation of atomic force microscopy,a multilayer film or three-dimensional structures were observed.It was interesting to note that the LB films of achiral compound Cu-NA with naphthyl segment and without methyl groups transferred from water surface showed chirality.The supramolecular chirality in the present LB films was suggested to be due to a cooperative stereoregular-stacking of the functional groups in a helical sense.This research work provides a helpful clue for regulating the nanostructures and supramolecular chiral assembly in organized films.展开更多
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.20675009 and No. 90922023）. The basis set aug-cc-pVDZ-PP for iodine atom is downloaded at the website http：//bse.pnl.gov/ bse/portal.
文摘The theoretical calculation and spectroscopic experiments indicate a kind of triangular three bonding supramolecular complexes CBr4…X^-…-H-C, which consist of carbon tetrabromide, halide, and protic solvent molecule （referring to dichloromethane, chloroform and acetonitrile）, can be formed in solution. The strength of halogen and hydrogen bonds in the triangular complexes using halide as common acceptor obeys the order of iodide〉bromide〉chloride. The halogen and hydrogen bonds work weak-cooperatively. Charge transfer bands of halogen bonding complexes between CBra and halide are observed in UV-Vis absorption spectroscopy in three solvents, and then the stoichiometry of 1：1, formation constants K and molar extinction coefficients ε of the halogen bonding complexes are obtained by Benesi-Hildebrand method. The K and ε show a dependence on the solvent dielectric constant and, on the whole, obey an order of iodide〉bromide〉chloride in the same solvents. Furthermore, the C-H vibrational frequencies of solvent molecules vary obviously with the addition of halide, which indicates the C-H…X- interaction. The experimental data indicate that the halogen bond and hydrogen bond coexist by sharing a common halide acceptor as predicted by calculation.
基金supported by the National Natural Science Foundation of China (Grant Nos. 20903078,21207112)the Natural Science Foundation of Hebei Province (Grant No. B2012203060)+4 种基金the China Postdoctoral Science Foundation (Grant Nos. 2011M500540,2012M510770)the Support Program for Hundred Excellent Innovation Talents from Universities and Colleges of Hebei Province (Grant No. CPRC020)the Science Foundation for the Excellent Youth Scholars from Universities and Colleges of Hebei Province (Grant No. Y2011113)the Scientific Research Foundation for Returned Overseas Chinese Scholars of Hebei Province (Grant No.2011052)the Open Foundation of State Key Laboratory of Solid Lubrication (Grant No. 1002)
文摘Four achiral Cu(Ⅱ)-coordinated Schiff bases complexes containing aromatic structures were synthesized and their supramolecular assemblies at the air/water interface were investigated.All the compounds could be spread on water surface although they have no alkyl chains.The Schiff base complex molecules with naphthyl groups tended to form J-aggregate in the Langmuir-Blodgett(LB) films transferred from water surface.By investigation of atomic force microscopy,a multilayer film or three-dimensional structures were observed.It was interesting to note that the LB films of achiral compound Cu-NA with naphthyl segment and without methyl groups transferred from water surface showed chirality.The supramolecular chirality in the present LB films was suggested to be due to a cooperative stereoregular-stacking of the functional groups in a helical sense.This research work provides a helpful clue for regulating the nanostructures and supramolecular chiral assembly in organized films.
