Switching rotaxane to pseudorotaxane by chemical signals: A crucial role of lateral repulsive interactions

Kód výsledku v IS VaVaI

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Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

Switching rotaxane to pseudorotaxane by chemical signals: A crucial role of lateral repulsive interactions

Popis výsledku v původním jazyce

Using the slippage approach,1 we prepared a cucurbit[6]uril (CB6)-based rotaxanes (R) with dissymmetric tritopic guests (L) consisting of iso-butylamine, 1,6-hexanediamine and adamantane-based (Ad) motif. The former two sites bind CB6 whereas the latter serves as a receptor for the CB7 signalling molecule. The synthesis of rotaxanes2 is shown in the Graphical abstract (GA, left). In studying the portal-portal interactions between macrocycles within R1, we found out, that the portal repulsions between the CB6 unit trapped in a rotaxane manner and CB7 at the Ad site significantly increase the free energy of the system to enable CB6 to overcome of the slip-off barrier. Thus, the rotaxane is transformed into dynamic pseudorotaxane (P1, GA, right). Moreover, the dynamics of the slip-off process can be modulated by the precise design of the adamantane binding site (R2 R5). Longer linkers between Ad and CB6 reduce the repulsion between CB7 and CB6 to decelerate the slipping-off (GA, graph). Our systems represent a nice example of a dual switch combining chemical and thermal stimuli.

Název v anglickém jazyce

Switching rotaxane to pseudorotaxane by chemical signals: A crucial role of lateral repulsive interactions

Popis výsledku anglicky

Using the slippage approach,1 we prepared a cucurbit[6]uril (CB6)-based rotaxanes (R) with dissymmetric tritopic guests (L) consisting of iso-butylamine, 1,6-hexanediamine and adamantane-based (Ad) motif. The former two sites bind CB6 whereas the latter serves as a receptor for the CB7 signalling molecule. The synthesis of rotaxanes2 is shown in the Graphical abstract (GA, left). In studying the portal-portal interactions between macrocycles within R1, we found out, that the portal repulsions between the CB6 unit trapped in a rotaxane manner and CB7 at the Ad site significantly increase the free energy of the system to enable CB6 to overcome of the slip-off barrier. Thus, the rotaxane is transformed into dynamic pseudorotaxane (P1, GA, right). Moreover, the dynamics of the slip-off process can be modulated by the precise design of the adamantane binding site (R2 R5). Longer linkers between Ad and CB6 reduce the repulsion between CB7 and CB6 to decelerate the slipping-off (GA, graph). Our systems represent a nice example of a dual switch combining chemical and thermal stimuli.

Druh

O - Ostatní výsledky

CEP obor

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OECD FORD obor

10401 - Organic chemistry

Projekt

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Návaznosti

S - Specificky vyzkum na vysokych skolach

Rok uplatnění

2023

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů