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991.
Synthesis and Predetermined Supramolecular Chirality of Carbohydrate‐Functionalized Perylene Bisimide Derivatives 下载免费PDF全文
Eight carbohydrate‐modified perylene bisimides ( PBI‐4 lac‐2 lac , PBI‐4 lac‐2 Man , PBI‐4 lac‐2 Gal , PBI‐4 lac‐2 Mal , PBI‐4 Man‐2 Man , PBI‐4 Man‐2 lac , PBI‐4 Man‐2 Gal and PBI‐4 Man‐2 Mal ) were synthesized, and the following predetermined supramolecular chirality rule was found: perylene bisimides modified with disaccharides (D ‐lactose and D ‐maltose) at the imide position generated right‐handed chirality, and those modified with monosaccharides (D ‐mannose and D ‐galactose) generated left‐handed chirality, when D ‐lactose or D ‐mannose was substituted in the bay positions of perylene bisimides with amide bonds as the linking spacers. These results may be because of the difference in the stacking angle of the perylene bisimide backbones induced by the steric effect and the additional hydrogen bonds between the disaccharide residues. This study provides an important design rule for predetermined chiral self‐assembly of perylene bisimides. 相似文献
992.
Driving Helical Packing of a Cyanine Dye on Dendron Nanofiber: Gel‐Shrinkage‐Triggered Chiral H‐Aggregation and Enhanced Enantiodiscrimination 下载免费PDF全文
Long Qin Fan Xie Xue Jin Prof. Minghua Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(32):11300-11305
An intelligent molecular hydrogel with a volume phase transition was constructed to regulate the chiral packing of a well‐known cyanine dye on a dynamically self‐assembled chiral nanofiber by using a pH trigger. During the shrinkage of the gel, the chiral nanofiber hierarchically assembled into a superhelix and simultaneously drove the dye molecules to stack, from a predominantly monomer form, in an unexpected helical H‐aggregation manner. Through such a transformation, the supramolecular chirality of the system was significantly enhanced and a new property of visual discrimination for chiral amines emerged. 相似文献
993.
Alam MZ Yoshioka T Ogata T Nonaka T Kurihara S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(9):2641-2647
Five photochromic chiral azobenzene compounds and one nonphotochromic chiral compound were synthesized and characterized by IR, 1H NMR spectroscopy, and elemental analysis. Cholesteric liquid crystalline phases were induced by mixing of the nonphotochromic chiral compound and one of the photochromic chiral azobenzene compounds in a host nematic liquid crystal (E44). The helical pitch of the induced cholesteric phase was determined by Cano's wedge method and the helical twisting power (HTP) of each sample was thus determined. The helical twisting powers of azobenzene compounds were decreased upon UV irradiation, due to trans-->cis photoisomerization of azobenzene molecules. Among the azobenzene compounds synthesized in our study, Azo-5, with isomannide (radical) as chiral photochromic dopant, showed the highest HTP and contrast ratio (Tmax/Tmin). Photoswitching between compensated nematic phase and cholesteric phase was achieved through reversible trans<-->cis photoisomerization of the chiral azobenzene molecules through irradiation with UV and visible light, respectively. Transmission rates (contrast ratios) increased with decreasing helical pitch length in the induced cholesteric phase. The influence of helical twisting power on the photoswitching behavior of chiral azobenzene compounds is discussed in detail. 相似文献
994.
995.
Das D Dasgupta A Roy S Mitra RN Debnath S Das PK 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(19):5068-5074
The water immobilization by a simple amino acid-containing cationic surfactant was investigated. A variety of techniques, such as (1)H NMR spectroscopy, circular dichroism (CD), steady-state fluorescence spectroscopy, and field-emission scanning electron microscopy (FESEM) were applied to determine the formation and architecture of the hydrogel. The new gelator with a minimum gelation concentration (MGC) of 0.3 % w/v shows prolonged stability and a low melting temperature (39 degrees C). (1)H NMR experiments revealed that intermolecular hydrogen bonding between the amide groups and pi-pi stacking of the indole rings are the two regulating parameters for gelation. Furthermore, fluorescence studies with 8-anilino-1-naphthalenesulfonic acid (ANS) as the probe indicate the participation of hydrophobicity during gelation. The luminescence study using both ANS and pyrene, along with FESEM results, indicate a critical concentration, well below the MGC, at which fibres begin to form. These cross-link further to give thicker fibers, leading to the formation of a hydrogel (0.3 % w/v). This new hydrogelator expresses high supramolecular chirality, as evidenced by the CD spectra. In addition, the gelator molecule was found to be nontoxic up to a concentration of 4 mM (0.2 % w/v). The high supramolecular chirality, prolonged stability, low melting point, and biocompatibility of the molecule make it a focus of chemical and biological interest. 相似文献
996.
D'Alessandro DM Topley AC Davies MS Keene FR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(18):4873-4884
Intervalence charge-transfer (IVCT) solvatochromism studies on the diastereoisomeric forms of [{Ru(bpy)(2)}(2)(mu-BL)](5+) (bpy=2,2'-bipyridine; BL=a series of di-bidentate polypyridyl bridging ligands) reveal that the solvent dependencies of the IVCT transitions decrease as the "tail" of the bridging ligand is extended, and the extent of delocalisation increases. Utilising a classical theoretical approach for the analysis of the intervalence charge-transfer (IVCT) solvatochromism data, the subtle and systematic variation in the electronic properties of the bridging ligands can be correlated with the shift between the localised (class II) and localised-to-delocalised (class II-III) regimes. The investigation of the diastereoisomeric forms of two series of complexes incorporating analogous structurally rigid (fused) and nonrigid (unfused) bridging ligands demonstrates that the differences in the IVCT characteristics of the diastereoisomers of a given complex are accentuated in the latter case, due to a stereochemically induced redox asymmetry contribution. The marked dependence of the IVCT transitions on the stereochemical identity of the complexes provides a quantitative measure of the fundamental contributions of the reorganisational energy and redox asymmetry to the intramolecular electron-transfer barrier at the molecular level. 相似文献
997.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(1):251-260
Terminally blocked, homo‐peptide amides of (R,R)‐1‐amino‐2,3‐diphenylcyclopropane‐1‐carboxylic acid (c3diPhe), a chiral member of the family of Cα‐tetrasubstituted α‐amino acids, from the dimer to the tetramer, and diastereomeric co‐oligopeptides of (R,R)‐ or (S,S)‐c3diPhe with (S)‐alanine residues to the trimer level were prepared in solution and fully characterized. The synthetic effort was extended to terminally protected co‐oligopeptide esters to the hexamer, where c3diPhe residues are combined with achiral α‐aminoisobutyric acid residues. The preferred conformations of the peptides were assessed in solution by FT‐IR absorption, NMR, and CD techniques, and for seven oligomers in the crystal state (by X‐ray diffraction) as well. This study clearly indicates that c3diPhe, a sterically demanding cyclopropane analogue of phenylalanine, tends to fold peptides into β‐turn and 310‐helix conformations. However, when c3diPhe is in combination with other chiral residues, the conformation preferred by the resulting peptides is also dictated by the chiral sequence of the amino acid building blocks. The (S,S)‐enantiomer of this α‐amino acid, unusually lacking asymmetry in the main chain, strongly favors the left‐handedness of the turn/helical peptides formed. 相似文献
998.
The triple ligand transfer reaction between planar-chiral cyclopentadienyl-ruthenium complexes [Cp′Ru(NCMe)3][PF6] (1) (Cp′ = 1-(COOR2)-2-Me-4-R1C5H2; R1 = Me, Ph, t-Bu) and iron complexes CpFe(CO)(L)X (2) (L = PMe3, PMe2Ph, PMePh2, PPh3; X = I, Br) resulted in the formation of metal-centered chiral ruthenium complexes Cp′Ru(CO)(L)X (3) in moderate yields with diastereoselectivities of up to 68% de. The configurations of some major diastereomers were determined to be by X-ray crystallography. The diastereoselectivity of 3 was under kinetic control and not affected by the steric effect of the substituents on the Cp′ ring of 1 and the phosphine of 2. Although the double ligand transfer reaction between [Cp′Ru{P(OMe)3}(NCMe)2][PF6] (7) and CpFe(CO)2X (8) produced Cp′Ru{P(OMe)3}(CO)X (9), the selectivity at the ruthenium center was low. 相似文献
999.
Optically enriched homo-binuclear Fischer chromium carbene complexes with planar chiral arene chromium complexes gave α-allyl β-arylpropionates up to 97% ee by reaction with allyl alkoxide and subsequent photo-oxidative demetalation. The chiral hetero-binuclear tungsten carbene complexes afforded anti α-allyl β-hydroxy β-arylpropionates as a major product up to 92/8 dr by the same reaction sequence. High diastereoselectivity in these reactions is contributed to the planar chirality of the arene chromium complex, even though the reaction was carried out under vigorous basic media. The reaction products, α-allyl β-arylpropionates were derived by 1,3-M(CO)5 shift and subsequent [3,3]-sigmatropic rearrangement. Also, the corresponding chromium-uncomplexed α,β-unsaturated Fischer carbene complexes afforded α-allyl β-arylpropionates under the same conditions. Formation of β-allyl β-arylpropionates via 1,2-M(CO)5 shift followed by [3,4]-sigmatropic rearrangement was not observed in both reactions of chromium-coordinated and the corresponding chromium-uncoordinated α,β-unsaturated Fischer carbene complexes with allyl alkoxide in the presence of base. 相似文献
1000.
Patrick J. M. Stals Maarten M. J. Smulders Rafael Martín‐Rapún Dr. Anja R. A. Palmans Dr. E. W. Meijer Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(9):2071-2080
Molecular organization : Chiral benzene tricarboxamides with methyl substituents at defined positions self‐assemble into supramolecular polymers of preferred helicity by three‐fold α‐helical‐type hydrogen bonding. The odd–even effect is operative and all derivatives are liquid crystalline showing a Colho phase (see figure).