10.1002/chem.201902898
Chemistry - A European Journal
FULL PAPER
The presence of a strong thermal hysteresis between the
assembly and disassembly processes is related to the existence
of a kinetic barrier during the aggregation process, thus offering
the possibility to delay the nucleation process and to reach
sigmoidal growth for temperatures comprised between Te and
Te’. This behavior relates here to the particular propeller shape
of the TATA molecules. It induces strong entropic and
conformational contributions to the self-assembly process which
relates to i) the breakage of the intramolecular rotation at the
nitrogen center of the C3-symmetric TATA, and to ii) the
heterochiral mismatch of their and conformers in the
stacking of the columnar polymers. We have also unraveled the
presence of divergent chiral self-assembly pathways that can
take place at a similar concentration and range of temperature
but for different cooling rates of the system. Kinetic analysis of
the CD melting curves, interpretation of VCD bisignate bands, as
well as AFM imaging here show together that the difference of
chirality is related to the formation of structures of higher
hierarchy (i.e. superhelices) which readily form upon slow
cooling. Such a large structural change obtained from such a
small thermal effect is of particular fundamental interest for
gaining knowledge and control over complex self-assembly
processes. This unprecedented observation of a hierarchical
bifurcation is possible because the system shows a peculiar
novelty compared to the other systems published so far in the
literature, as the kinetic product (single P-helix) is thermally
stable for a long time without conversion to the thermodynamic
product (P-helix M-superhelix), so as it can be properly
isolated and characterized. The reason of this stability relates to
the very low kinetic lability of TATA molecules in the primary
stacks, as well as to their locked conformation as P propellers in
the single helix (as shown by the strong memory effect
deciphered here). This feature is also of potential practical
interest for fine-tuning the physical properties of functional
materials of these systems.[9]
Innovations (NWO Project Nr. 731.014.209). We wish to thank
the international center for Frontier Research in Chemistry
(icFRC), the Laboratory of Excellence for Complex Systems
Chemistry (LabEx CSC), and the Institut Universitaire de France
(IUF) for financial support. We also acknowledge the Electron
Microscopy Facility of the Institut Charles Sadron.
Keywords: supramolecular polymers • hierarchical self-
assembly • pathway complexity • organogelators
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