Redox-controlled hybridization of helical foldamers

Faour, Lara; Adam, Catherine; Gautier, Christelle; Goeb, Sébastien; Allain, Magali; Levillain, Eric; Canevet, David; Sallé, Marc

doi:10.1039/c9cc02498k

Cited by 19 publications

(14 citation statements)

References 45 publications

(52 reference statements)

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“…The dissociation of the dimer is further supported by a 1 H DOSY NMR experiment recorded at c =3⋅10 −5 m from which a diffusion coefficient of D =3.63⋅10 −10 m 2 s −1 was extracted (Figure S14), a value similar to that observed for the monomer OxM 4 L 2 tweezer ( D =3.31⋅10 −10 m 2 s −1 , Figures and S6). The slow equilibrium between the monomer and the dimer species at the NMR timescale allowed a straightforward determination of the dimerization constant K dim (MeOD)=(4.4±0.2)⋅10 3 (Figure S18) …”

Section: Figurementioning

confidence: 99%

“…Thes low equilibrium between the monomer and the dimer species at the NMR timescale allowed as traightforward determination of the dimerization constant K dim (MeOD) = (4.4 AE 0.2)·10 3 (Figure S18). [16] To further study the stability of the dimeric (NaphM 4 L 2 ) 2 species,w ei nvestigated its behavior in the presence of DCTNF,a ne lectron-poor unit known to interact strongly with electron-rich derivatives. [17] Interestingly,u pon addition of 4equiv of DCTNF to as olution of (NaphM 4 L 2 ) 2 (c = 10 À3 m,MeOD), the 1 HNMR spectrum appeared significantly simplified (Figure 5d), illustrating the dissociation of the dimeric species.M oreover,t he resulting a and b protons showed chemical shifts similar to those of the NaphM 4 L 2 monomer (Figure 5c), while signals corresponding to the DTF core were upfield-shifted.…”

Section: Meod At 298 K(figures 5a-c and S13mentioning

confidence: 99%

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Metalla‐Assembled Electron‐Rich Tweezers: Redox‐Controlled Guest Release Through Supramolecular Dimerization

et al. 2019

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Developing methodologies for on‐demand control of the release of a molecular guest requires the rational design of stimuli‐responsive hosts with functional cavities. While a substantial number of responsive metallacages have already been described, the case of coordination‐tweezers has been less explored. Herein, we report the first example of a redox‐triggered guest release from a metalla‐assembled tweezer. This tweezer incorporates two redox‐active panels constructed from the electron‐rich 9‐(1,3‐dithiol‐2‐ylidene)fluorene unit that are facing each other. It dimerizes spontaneously in solution and the resulting interpenetrated supramolecular structure can dissociate in the presence of an electron‐poor planar unit, forming a 1:1 host–guest complex. This complex dissociates upon tweezer oxidation/dimerization, offering an original redox‐triggered molecular delivery pathway.

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Section: Figurementioning

confidence: 99%

Section: Meod At 298 K(figures 5a-c and S13mentioning

confidence: 99%

Metalla‐Assembled Electron‐Rich Tweezers: Redox‐Controlled Guest Release Through Supramolecular Dimerization

et al. 2019

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“…Both the selectivity and reversibility of anion binding (Cl − or HSO 4 − ) to electropositive amide protons within the internal cavity could be demonstrated. A strictly related foldamer, in which the thiol anchoring point was substituted with an isobutyl chain, was either chemically or electrochemically oxidized with thianthrenium tetrafluoroborate, thus generating radical cations at both tetrathiafulvalene redox centers [ 168 ]. As a result, spectroelectrochemical analyses of variations in UV–vis absorption spectra evidenced that the weak dimerization tendency for the neutral species in 1:1 CH 2 Cl 2 /CH 3 CN was increased by a factor of ~100 for diradical dications, even though the exact arrangement was not determined.…”

Section: Aromatic Foldamersmentioning

confidence: 99%

The Diverse World of Foldamers: Endless Possibilities of Self-Assembly

Rinaldi

2020

Molecules

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Different classes of foldamers, which are synthetic oligomers that adopt well-defined conformations in solution, have been the subject of extensive studies devoted to the elucidation of the forces driving their secondary structures and their potential as bioactive molecules. Regardless of the backbone type (peptidic or abiotic), the most important features of foldamers are the high stability, easy predictability and tunability of their folding, as well as the possibility to endow them with enhanced biological functions, with respect to their natural counterparts, by the correct choice of monomers. Foldamers have also recently started playing a starring role in the self-assembly of higher-order structures. In this review, selected articles will be analyzed to show the striking number of self-assemblies obtained for foldamers with different backbones, which will be analyzed in order of increasing complexity. Starting from the simplest self-associations in solution (e.g., dimers of β-strands or helices, bundles, interpenetrating double and multiple helices), the formation of monolayers, vesicles, fibers, and eventually nanostructured solid tridimensional morphologies will be subsequently described. The experimental techniques used in the structural investigation, and in the determination of the driving forces and mechanisms underlying the self-assemblies, will be systematically reported. Where applicable, examples of biomimetic self-assembled foldamers and their interactions with biological components will be described.

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“…Oxidation in solution of TTF derivatives 5,6 into the corresponding -dimer species (TTF •+ )2 has been characterized in very specific cases, i.e. highly concentrated solutions at low temperature, 7,8 redox-active units confined in a molecular cavity, [9][10][11][12] covalently preorganized poly-TTF systems, [13][14][15][16][17][18][19][20][21][22] or stabilization of TTF units in interlocked structures. 1,23 To get a better control over the experimental parameters driving the radical-pairing interaction, there is a need to develop new molecular models.…”

Section: Introductionmentioning

confidence: 99%