Distance Matters: Biasing Mechanism, Transfer of Asymmetry, and Stereomutation in N-Annulated Perylene Bisimide Supramolecular Polymers

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Martínez, Manuel A. and Doncel Giménez, Azahara and Cerdá, Jesús and Calbo, Joaquín and Rodríguez, Rafael and Aragó, Juan and Crassous, Jeanne and Ortí, Enrique and Sánchez Martín, Luis (2021) Distance Matters: Biasing Mechanism, Transfer of Asymmetry, and Stereomutation in N-Annulated Perylene Bisimide Supramolecular Polymers. Journal of the American Chemical Society, 143 (33). pp. 13281-13291. ISSN 0002-7863

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Official URL: https://doi.org/10.1021/jacs.1c06125




Abstract

The synthesis of two series of N-annulated perylene bisimides (PBIs), compounds 1 and 2, is reported, and their selfassembling features are thoroughly investigated by a complete set of spectroscopic measurements and theoretical calculations. The study corroborates the enormous influence that the distance between the PBI core and the peripheral groups exerts on the chiroptical properties and the supramolecular polymerization mechanism. Compounds 1, with the peripheral groups separated from the central PBI core by two methylenes and an ester group, form J-type supramolecular polymers in a cooperative manner but exhibit negligible chiroptical properties. The lack of clear helicity, due to the staircase arrangement of the self-assembling units in the aggregate, justifies these features. In contrast, attaching the peripheral groups directly to the N-annulated PBI core drastically changes the self-assembling properties of compounds 2, which form H-type aggregates following an isodesmic mechanism. These Htype aggregates show a strong aggregation-caused quenching (ACQ) effect that leads to nonemissive aggregates. Chiral (S)-2 and (R)-2 experience an efficient transfer of asymmetry to afford P- and M-type aggregates, respectively, although no amplification of asymmetry is achieved in majority rules or “sergeants-and-soldiers” experiments. A solvent-controlled stereomutation is observed for chiral (S)-2 and (R)-2, which form helical supramolecular polymers of different handedness depending on the solvent (methylcyclohexane or toluene). The stereomutation is accounted for by considering the two possible conformations of the terminal phenyl groups, eclipsed or staggered, which lead to linear or helical self-assemblies, respectively, with different relative stabilities depending on the solvent.


Item Type:Article
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CRUE-CSIC (Acuerdos Transformativos 2021)

Uncontrolled Keywords:Circular dichroism spectroscopy, Optical properties, Aromatic compounds, Solvents, Polymers
Subjects:Sciences > Chemistry > Chemistry, Organic
ID Code:69342
Deposited On:21 Dec 2021 11:16
Last Modified:22 Feb 2022 10:50

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