Unconventional Chiral Amplification in Luminescent Supramolecular Polymers Based on Trisbiphenylamine-tricarboxamides

Dorca, Yeray; Naranjo, Cristina; Ghosh, Goutam; Gómez, Rafael; Fernández, Gustavo; Sánchez, Luis

doi:10.1055/s-0040-1705124

Cited by 5 publications

(6 citation statements)

References 16 publications

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“…However, an analogous effect but of opposite sign is observed for the SaS experiments carried out by mixing 1 and ( S ) - 1 (Figure S18). We have previously described a similar effect for self-assembling units able to form intramolecular hydrogen-bonded metastable monomers that retard the corresponding supramolecular polymerization . However, this is not the case, since N-annulated PBIs 1 cannot form H-bonded metastable monomers and their supramolecular polymerization is under thermodynamic control.…”

Section: Resultsmentioning

confidence: 98%

“…We have previously described a similar effect for self-assembling units able to form intramolecular hydrogen-bonded metastable monomers that retard the corresponding supramolecular polymerization. 25 However, this is not the case, since N-annulated PBIs 1 cannot form H-bonded metastable monomers and their supramolecular polymerization is under thermodynamic control. A similar abnormal SaS effect has been described for covalent polymers and justified by considering the different energy preferences exhibited by the situation in which a chiral sergeant is adjacent to another chiral sergeant or to an achiral soldier.…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2021

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The synthesis of two series of N-annulated perylene bisimides (PBIs), compounds 1 and 2 , is reported, and their self-assembling 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 H-type 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.

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Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

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

et al. 2021

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“…Such cores have already demonstrated their potential as optoelectronic 31 and supramolecular materials. 32 − 34 …”

Section: Resultsmentioning

confidence: 99%

“…Thus, we opted for a partially O -bridged triphenylborane ( S -B1 ) whose electron-rich environment and structural rigidity impart higher stability to the boron center when compared to those of nonbridged analogues. ,, Bridged triarylboranes have been recently introduced as a new class of stable, organic electronic materials by one of us. , On the basis of the design of S -B1 , two N cores were synthesized: (i) an analogous partially O -bridged triphenylamine, S -N1 , and (ii) a triphenylamine core, S -N2 and a-N2 . Such cores have already demonstrated their potential as optoelectronic and supramolecular materials. − …”

Section: Resultsmentioning

confidence: 99%

Long-Lived Charge-Transfer State from B–N Frustrated Lewis Pairs Enchained in Supramolecular Copolymers

et al. 2020

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The field of supramolecular polymers is rapidly expanding; however, the exploitation of these systems as functional materials is still elusive. To become competitive, supramolecular polymers must display microstructural order and the emergence of new properties upon copolymerization. To tackle this, a greater understanding of the relationship between monomers’ design and polymer microstructure is required as well as a set of functional monomers that efficiently interact with one another to synergistically generate new properties upon copolymerization. Here, we present the first implementation of frustrated Lewis pairs into supramolecular copolymers. Two supramolecular copolymers based on π-conjugated O -bridged triphenylborane and two different triphenylamines display the formation of B–N pairs within the supramolecular chain. The remarkably long lifetime and the circularly polarized nature of the resulting photoluminescence emission highlight the possibility to obtain an intermolecular B–N charge transfer. These results are proposed to be the consequences of the enchainment of B–N frustrated Lewis pairs within 1D supramolecular aggregates. Although it is challenging to obtain a precise molecular picture of the copolymer microstructure, the formation of random blocklike copolymers could be deduced from a combination of optical spectroscopic techniques and theoretical simulation.

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“…In 1989, Green and co-workers reported that copolymers of an achiral isocyanate with a small fraction of a chiral isocyanate exhibit a disproportionate helical bias. This phenomenon is called the sergeants-and-soldiers (S&S) effect, − and numerous subsequent studies have shown that it is applicable to both covalent − and supramolecular − polymers.…”

Section: Introductionmentioning

confidence: 99%

Biasing the Screw-Sense of Supramolecular Coassemblies Featuring Multiple Helical States

et al. 2020

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By enchaining a small fraction of chiral monomer units, the helical sense of a dynamic polymer constructed from achiral monomer units can be disproportionately biased. This phenomenon, known as the sergeants-and-soldiers (S&S) effect, has been found to be widely applicable to dynamic covalent and supramolecular polymers. However, it has not been exemplified with a supramolecular polymer that features multiple helical states. Herein, we demonstrate the S&S effect in the context of the temperature-controlled supramolecular copolymerization of chiral and achiral biphenyl tetracarboxamides in alkanes. The one-dimensional helical structures presented in this study are unique because they exhibit three distinct helical states, two of which are triggered by coassembling with monomeric water that is codissolved in the solvent. The self-assembly pathways are rationalized using a combination of mathematical fitting and simulations with a thermodynamic mass-balance model. We observe an unprecedented case of an “abnormal” S&S effect by changing the side chains of the achiral soldier. Although the molecular structure of these aggregates remains elusive, the coassembly of water is found to have a profound impact on the helical excess.

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Unconventional Chiral Amplification in Luminescent Supramolecular Polymers Based on Trisbiphenylamine-tricarboxamides

Cited by 5 publications

References 16 publications

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

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

Long-Lived Charge-Transfer State from B–N Frustrated Lewis Pairs Enchained in Supramolecular Copolymers

Biasing the Screw-Sense of Supramolecular Coassemblies Featuring Multiple Helical States

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