Dimeric capsule vs columnar polymer: Structural factors determining the aggregation behavior of amino acid functionalized benzene-1,3,5-tricarboxamides in solution and in the solid-state

Perlitius, Filip; Walczak, Anna; Čonková, Miroslava; Markiewicz, Grzegorz; Harrowfield, Jack; Stefankiewicz, Artur R.

doi:10.1016/j.molliq.2022.120511

Cited by 8 publications

(9 citation statements)

References 48 publications

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“…Importantly, these aggregates are not significant for the same solution containing a higher fraction of BTA ( S )‐Cha (fs 0 =39 %). SANS curves for the solutions with fs 0 =39 % are fitted considering a mixture of cylindrical objects, for BTA P (or BTA P ⋅[Cu]) and BTA ( S )‐Cha helical co‐assemblies, and spherical objects, for BTA ( S )‐Cha dimers [68–73] . Good fits are obtained by assuming a radius for the cylinders (11±1 Å) that is consistent with a single BTA molecule in the cross‐section, i. e. single helices (see the experimental section for more details and Figure S6 for the SANS curves of the individual components) [60] .…”

Section: Resultsmentioning

confidence: 99%

“…SANS curves for the solutions with fs 0 = 39 % are fitted considering a mixture of cylindrical objects, for BTA P (or BTA P•[Cu]) and BTA (S)-Cha helical co-assemblies, and spherical objects, for BTA (S)-Cha dimers. [68][69][70][71][72][73] Good fits are obtained by assuming a radius for the cylinders (11 � 1 Å) that is consistent with a single BTA molecule in the cross-section, i. e. single helices (see the experimental section for more details and Figure S6 for the SANS curves of the individual components). [60] The fraction of BTA (S)-Cha that is actually present in the stacks, fs s , can also be extracted from these fits: fs s = 36 % and 25 % for helical co-assemblies with and without [Cu], respectively.…”

Section: Chemistry-a European Journalmentioning

confidence: 97%

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Rationalizing the Extent of the “Sergeants‐and‐Soldiers” Effect in Supramolecular Helical Catalysts: Effect of Copper Coordination

Hammoud

Martínez‐Aguirre

et al. 2023

Chemistry A European J

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Aggregation of supramolecular helices, for example through interdigitation of their alkyl side chains or through more directional supramolecular interactions, leads to hierarchical architectures with original structural and chiroptical properties. However, when a chiral monomer (the "sergeant") is introduced as a minor component in these assemblies composed of a majority of achiral monomers (the "soldiers"), it is not clear how the aggregation changes the ability of the sergeant to induce a preferential helicity to the polymer main chain (the so-called "sergeants-and-soldiers" effect). This study reports a detailed investigation of the influence of [Cu(OAc) 2 •H 2 O] coordination on the structure and chiroptical properties of helical hydrogen-bonded co-assemblies composed of a catalytically-active benzene-1,3,5-tricarboxamide (BTA) monomer, acting as the "soldier", and an enantiopure BTA monomer derived from cyclohexylalanine, playing the role of the "sergeant". The copper actually significantly influences the extent of the "sergeants-and-soldiers" effect since it acts as a crosslink that induces some chiral defects in the supramolecular helices. These crosslinks appear to be preserved during the catalytic hydrosilylation of 4-nitroacetophenone. The aggregation of helices through the formation of copper crosslinks is reversible since homochiral single helices are exclusively formed in the case of sergeant-rich assemblies. The fact that both main chain and side chain aggregation affects the chiroptical properties of supramolecular helices must be considered in the design of elaborated chiral materials.

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Section: Resultsmentioning

confidence: 99%

Section: Chemistry-a European Journalmentioning

confidence: 97%

Rationalizing the Extent of the “Sergeants‐and‐Soldiers” Effect in Supramolecular Helical Catalysts: Effect of Copper Coordination

Hammoud

Martínez‐Aguirre

et al. 2023

Chemistry A European J

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“…There are several researches mentioning the substituent effects on the formation of selfassembled structures. [38][39][40][41][42] Scheme 1. Synthesis of TBIB-A L , TBIB-V L , TBIB-V D and TBIB-G.…”

Section: Resultsmentioning

confidence: 99%

Amino‐Acid Based Chiral Trisubstituted Benzimidazole Supramolecules: Synthesis and Self‐Assembling Behavior

Mizukoshi

Sogawa

Sanda

2023

Chemistry A European J

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Trisubstituted 1,3,5‐tri(benzimidazolyl)benzene derivatives were synthesized from l‐alanine, l‐valine, d‐valine and glycine, and their self‐assembling behavior and stimuli‐response in solution and gel states were evaluated. Circular dichroism/UV‐vis absorption spectroscopic and dynamic light scattering measurements revealed that the compounds formed H‐aggregates via intramolecular hydrogen bonding and π‐π stacking interactions in nonpolar solvents such as CHCl3, whereas collapse of the aggregates was confirmed by MeOH addition. Quantum mechanical calculations and molecular dynamics simulations also supported aggregation in CHCl3. Rheological analysis and morphology observation revealed the formation of a fibril like structure by further assembling of aggregates at a high concentration in CHCl3.

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“…Factors such as solvent viscosity, 22 molecular cyclization, 23 hostguest interactions, 24 hydrogen bonding. 18 and many others 25,26 have also been recognized as important influences on aryl group rotation.…”

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confidence: 99%

“…S18 in ESI †). 26,30 The inherent chirality of 1 means that measurements of rotational strength can be applied to study of its aggregation behaviour. In particular, the circular dichroism (CD) spectrum of 1 in TCE shows a very marked temperature dependence, indicating that it could be used as a sensitive quantitative measure of the monomer-dimer equilibrium (Fig.…”

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confidence: 99%

Self-assembly of a fluorescent hydrogen-bonded capsule based on an amino-acid functionalised tetraphenylethylene

et al. 2023

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Dimeric capsule vs columnar polymer: Structural factors determining the aggregation behavior of amino acid functionalized benzene-1,3,5-tricarboxamides in solution and in the solid-state

Cited by 8 publications

References 48 publications

Rationalizing the Extent of the “Sergeants‐and‐Soldiers” Effect in Supramolecular Helical Catalysts: Effect of Copper Coordination

Rationalizing the Extent of the “Sergeants‐and‐Soldiers” Effect in Supramolecular Helical Catalysts: Effect of Copper Coordination

Amino‐Acid Based Chiral Trisubstituted Benzimidazole Supramolecules: Synthesis and Self‐Assembling Behavior

Self-assembly of a fluorescent hydrogen-bonded capsule based on an amino-acid functionalised tetraphenylethylene

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