Twists and turns in the hierarchical self-assembly pathways of a non-amphiphilic chiral supramolecular material

Abstract

The formation of helical self-assembled fibres by a C(3) symmetric molecule incorporating three tetrathiafulvalene units is shown to be influenced dramatically by the processing conditions, leading to a variety of different chiral forms, including unprecedented croissants.

Controlling supramolecular polymerization through multicomponent self‐assembly

“…These could be reduced by the addition of what the authors call a chain terminator, a monofunctional (N-methyl)imidazolyl Znporphyrin. In the light of recent developments in manipulating the kinetic stabilities and kinetic pathways in selfassembled supramolecular complexes [128][129][130][131][132][133][134][135][136] and supramolecular polymers, 22,[30][31][32][33][34][35][36][37][38][39][40][41][42]130,[137][138][139][140][141][142][143][144][145] it is interesting to note, that the addition of the chain stopper to the polymers did not lead to instantaneous disassembly. 127 The expected depolymerization and shortening of the polymers based on the comonomer feed ratio was only observed when the di-and monofunctional comonomers were premixed in a good FIGURE 3 (a) Chemical structures for the bi-and monofunctional phosphine ligands, P(Phe) 2 C 12 (Phe) 2 P and P(Phe) 2 C 12 , in order to prepare palladium(II)-based coordination polymers.…”

Hierarchical Self‐Assembly of Supramolecular Helical Fibres from Amphiphilic C3‐Symmetrical Functional Tris(tetrathiafulvalenes)

“…The particles are between one and two micrometres in width and between four and seven micrometres in length, the aspect ratio being similar in all cases. Often, the objects appear to be homochiral (see the optical microscope image in Figure 7), as they are clearly in the case of the chiral croissant‐shaped objects formed under similar conditions in dioxane for the compound B with the 2‐methyl‐butyl chain 36. However, the SEM images show that there is a non‐infrequent inversion of helicity.…”

“…33 To prepare electroactive supramolecular aggregates, we have recently attached thioalkyl containing TTF units to the 3,3′‐bis(acylamino)‐2,2′‐bipyridine‐substituted benzene‐1,3,5‐tricarboxamide (BiPy‐BTA) moieties. Accordingly, organogels and conducting xerogel upon doping have been obtained with three achiral bis(thioethyl)TTF fragments (compound A in Figure 1),34 while by the use of non‐amphiphilic chiral 2‐methyl‐butyl groups (compound B in Figure 1), helical fibres35 or microscopic croissants36 formed in the solid state depending on the preparation conditions. Experimental CD studies combined with theoretical CD calculations and molecular mechanics and dynamics modelling clearly demonstrated that for the ( S ) configuration of the alkyl chains the primary fibres in solution were of left‐handed ( M ) helicity, while inversion of the helical sense occurred from the solution to the solid state 35.…”

Oligopeptide‐Assisted Self‐Assembly of Oligothiophenes: Co‐Assembly and Chirality Transfer

“…To guarantee the accuracy of the measurement, the films were placed perpendicular to the light path and rotated with a constant speed within the film plane to avoid polarization-dependent reflections and eliminate the possible angle dependence of the CD signal. [45,46] Very interestingly, the intensity of the CD absorption at l = 228 nm was greatly suppressed for QT@P, whereas for QTDA@P this peak remained visible without any change. [36a, 42, 43] Weak but clear Cotton effects were observed at l = 437 nm for QT@P and l = 524 nm for QTDA@P (Figure 5 c, d), which indicated that chirality transfer to oligothiophene did occur through the weak interaction from the oligopeptide.…”