Cooperative supramolecular polymerization and amplification of chirality in C3-symmetrical OPE-based trisamides.
Sergeants-and-soldiers experiments demonstrate the amplification of chirality that transforms the racemic mixture of helical columns formed from OPE-based trisamides into enantiomerically enriched helical structures (see scheme).The cooperative supramolecular polymerization of the trisamides is investigated by theoretical calculations and temperature-dependent UV/Vis and CD experiments. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Helical supramolecular polymerization of C3-symmetric amides and retroamides: on the origin of cooperativity and handedness.
The cooperative supramolecular polymerization of 1 and 2 yields P- or M-type helical aggregates depending on the absolute configuration (S or R) of the stereogenic centres attached to the side chains. The connectivity of the amide group does not affect the handedness of the helical aggregates, but determines a larger cooperativity for retroamides 1.
On the handedness of helical aggregates of C3 tricarboxamides: a multichiroptical characterization
A complete chiroptical characterization of the supramolecular polymers formed by tricarboxamides (S)-1 and (R)-1 is performed using ECD, VCD and CPL dichroic techniques. The helical aggregates show an intense CPL signal and their absolute P- or M-configuration is assigned with the help of theoretical calculations.
A bis(triazole)benzamide receptor for the complexation of halide anions and neutral carboxylic acid guests. Guest-controlled topicity and self-assembly
Bis(triazole)benzamide 1 has been readily synthesized by means of Cu-catalyzed 1,3-dipolar cycloaddition and its ability to bind halide anions and neutral gallic acid derivative 12GA has been theoretically and experimentally investigated. The cavity defined by the N-H amide group and the vicinal aromatic hydrogens is suitable to form H-bonding arrays with halide guests. The stability of complexes 1·Cl- and 1·Br- is very similar, as DFT calculations predict and 1H NMR titration experiments confirm. The zigzag "anti" conformation of the molecule generates two regions with complementary positive and negative potentials that favor the statistical complexation of two molecules of the neutral car…
Tuning the Self-Assembly of Rectangular Amphiphilic Cruciforms
The self-assembly of a series of nonionic amphiphilic cruciforms based on the 1,2,4,5-tetrakis(phenylethynyl)benzene (TPEB) skeleton, in which the peripheral substituents have been modified to modulate the morphology of the supramolecular structures, is reported. The presence of linear paraffinic and hydrophilic chains in TPEBs 1 and 2 gives rise to two-dimensional structures of high aspect ratio. In contrast, the incorporation of dendronized hydrophilic chains results in the formation of twisted ribbons in amphiphile 3 and impedes the organized self-assembly of TPEB 4. Theoretical calculations show that the self-assembly of these amphiphiles might be initiated with the formation of π-stack…