Yeray Dorca

The kinetically controlled amplification of asymmetry experienced in the co-assembly of chiral tribiphenylaminetricarboxamides (S)-1 and (R)-1 is investigated. The formation of metastable monomeric species through intramolecular H-bonds retards the efficient amplification of asymmetry due to a chain-capper effect.

A comparative investigation of the chiral amplification features of a series of three families of C₃‐symmetric tricarboxamides, 1,3,5‐triphenylbenzenetricarboxamides (TPBAs), benzenetricarboxamides (BTAs) and oligo(phenylene ethynylene) tricarboxamides (OPE‐TAs), is here reported. As previously observed for BTAs and OPE‐TAs, a similar dichroic response is obtained for TPBAs decorated with one, two or three chiral side chains bearing stereogenic centers, thus confirming the efficient transfer of point chirality to the supramolecular helical aggregates. Unlike BTAs and OPE‐TAs, the chiral amplification ability of TPBAs in majority rules experiments shows a negligible dependence on the number of chiral centers per monomeric unit, and stands the largest among the series of tricarboxamides. Detailed experimental and theoretical studies demonstrate that the rotation angle between the TPBA units in the helical stack is intermediate to that observed for BTAs and OPE‐TAs. This feature strongly conditions the steric interactions between vicinal molecules in the stack and the final chiral amplification outcome. Furthermore, theoretical calculations show that achiral side chains favor the interdigitation of the helical aggregates and thereby the formation of bundle superstructures.

We describe the synthesis of two propeller-shaped, emissive trisbiphenylamines 1 and (S)-2. Whilst achiral 1 forms supramolecular polymers following a cooperative mechanism, the self-assembly of chiral (S)-2 can be described by an isodesmic mechanism. Despite the isodesmic character of the supramolecular polymerization of (S)-2, an efficient transfer of chirality from the embedded point chirality of the peripheral side chains to the aggregates is demonstrated. The co-assembly of 1 and (S)-2 in a sergeants-and-soldiers experiment shows a very different dichroic response to that registered for pristine (S)-2, with a copolymerization curve displaying two transitions. Both these transitions coincide with those observed for the pristine achiral and chiral components, thus suggesting a self-sorting effect.

Pathway‐Complexity, hierarchische Organisation, Außer‐Equilibrium‐ und metastabile oder kinetisch gefangene Spezies sind Begriffe die in jüngsten, hochqualitativen Publikationen im Feld der supramolekularen Polymere häufig verwendet werden. Oftmals sind die Terminologien, die die verschiedenen Selbstassemblierungspfade, die beteiligten Spezies und deren Beziehung sowie relativen Stabilitäten zueinander beschreiben, nicht trivial. In der Literatur sind häufig verschiedene Begriffe und Klassifizierungen zu finden, in vielen Fällen jedoch ohne klare Definitionen oder Richtlinien wie sie zu benutzen sind oder wie sie experimentell unterschieden werden können. Ziel dieses Kurzaufsatzes ist es, die existierenden Konzepte mithilfe jüngster Literatur zu klassifizieren, differenzieren und zu korrelieren. Dadurch soll der Leser eine generelle Einsicht in thermodynamische und kinetische Aspekte komplexer supramolekularer Polymerisationsprozesse erhalten. Ein gutes Verständnis dieser Begriffe und Konzepte sollte dazu beitragen, neue, komplexe, funktionale Materialien zu erschaffen.

Pathway complexity, hierarchical organization, out of equilibrium, and metastable or kinetically trapped species are common terms widely used in recent, high‐quality publications in the field of supramolecular polymers. Often, the terminologies used to describe the different self‐assembly pathways, the species involved, as well as their relationship and relative stability are not trivial. Different terms and classifications are commonly found in the literature, however, in many cases, without clear definitions or guidelines on how to use them and how to determine them experimentally. The aim of this Minireview is to classify, differentiate, and correlate the existing concepts with the help of recent literature reports to provide the reader with a general insight into thermodynamic and kinetic aspects of complex supramolecular polymerization processes. A good comprehension of these terms and concepts should contribute to the development of new complex, functional materials.