Chiroptical inversion of a planar chiral redox-switchable rotaxane

Gaedke, Marius; Witte, Felix; Anhäuser, Jana; Hupatz, Henrik; Schröder, Hendrik V.; Valkonen, Arto; Rissanen, Kari; Lützen, Arne; Paulus, Beate; Schalley, Christoph A.

doi:10.1039/c9sc03694f

Cited by 58 publications

(53 citation statements)

References 81 publications

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“…Only axle fragments are observed while the intact axle is not seen among the fragments (Figures S15 and S16 in Supporting Information File 1 ). This clearly supports the mechanically interlocked structure for NDIRot in analogy to similar structures investigated by tandem mass spectrometry earlier [ 35 , 40 ].…”

Section: Resultssupporting

confidence: 89%

“…Furthermore, a diastereotopic splitting of the crown ether methylene protons and downfield shifts of the axle methylene protons H d and H f clearly point at the rotaxane formation. Additionally, a strong upfield shift observed for the resonance of the phenylic proton H h (Δδ = 0.5 ppm) is in line with rotaxane formation, even though it has not previously been observed for similar TTF-containing rotaxanes [ 35 , 40 ]. This finding indicates a different conformation of the macrocycles in the NDI and TTF [2]rotaxanes.…”

Section: Resultsmentioning

confidence: 61%

“…Yet, keeping the formal C 2 -symmetry of the macrocycle is important to avoid mixtures of isomers upon the threading of directional axles, such as A1· PF 6 ( Fig. 1 ) [ 40 ]. Consequently, we chose to use a resorcinol-connected crown ether motif introduced by Stoddart and co-workers [ 44 ] for the NDI-crown-8 NDIC8 ( Fig.…”

Section: Resultsmentioning

confidence: 99%

“… a ITC titrations cannot be fitted to a 1:1 pseudo[2]rotaxane binding model (for details, see text below and Supporting Information File 1 , Figure S5). b Taken from a previous report [ 40 ]. …”

Section: Resultsmentioning

confidence: 99%

“…1 ). Several TTFC8 -derived molecular assemblies have been studied and provided access to new switching modes [ 35 – 36 38 ] and emergent optoelectronic properties [ 35 – 36 39 – 40 ], demonstrating the great potential of tailor-made redox-active crown ethers for the development of new molecular switches.…”

Section: Introductionmentioning

confidence: 99%

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Thermodynamic and electrochemical study of tailor-made crown ethers for redox-switchable (pseudo)rotaxanes

Hupatz¹,

Gaedke²,

Schröder³

et al. 2020

Beilstein J. Org. Chem.

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Crown ethers are common building blocks in supramolecular chemistry and are frequently applied as cation sensors or as subunits in synthetic molecular machines. Developing switchable and specifically designed crown ethers enables the implementation of function into molecular assemblies. Seven tailor-made redox-active crown ethers incorporating tetrathiafulvalene (TTF) or naphthalene diimide (NDI) as redox-switchable building blocks are described with regard to their potential to form redox-switchable rotaxanes. A combination of isothermal titration calorimetry and voltammetric techniques reveals correlations between the binding energies and redox-switching properties of the corresponding pseudorotaxanes with secondary ammonium ions. For two different weakly coordinating anions, a surprising relation between the enthalpic and entropic binding contributions of the pseudorotaxanes was discovered. These findings were applied to the synthesis of an NDI-[2]rotaxane, which retains similar spectroelectrochemical properties compared to the corresponding free macrocycle. The detailed understanding of the thermodynamic and electrochemical properties of the tailor-made crown ethers lays the foundation for the construction of new types of molecular redox switches with emergent properties.

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Section: Resultssupporting

confidence: 89%

Section: Resultsmentioning

confidence: 61%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Thermodynamic and electrochemical study of tailor-made crown ethers for redox-switchable (pseudo)rotaxanes

Hupatz¹,

Gaedke²,

Schröder³

et al. 2020

Beilstein J. Org. Chem.

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A Multiple Chirality Switching Device for Spatial Light Modulators

Yang

et al. 2020

Angewandte Chemie

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A new and simple strategy towards electric-fielddriven multiple chirality switching device has been designed and fabricated by combining a newly synthesized baseresponsive chiroptical polymer switch (R-FLMA) and pbenzoquinone (p-BQ) via proton-coupled electron transfer (PCET) mechanism. Clear and stable triple chirality states (silence, positive, negative) of this device in visible band can be regulated reversibly (> 1000 cycles) by adjusting voltage programs. Furthermore, such chiral switching phenomena are also accompanied by apparent changes of color and fluorescence. More importantly, the potential application of this device for a spatial light modulator has also been demonstrated.

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AIE‐Active Chiral [3]Rotaxanes with Switchable Circularly Polarized Luminescence

Wang

et al. 2021

Angewandte Chemie

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The construction of circularly polarized luminescence (CPL) switches with multiple switchable emission states and high dissymmetry factors (glum) has attracted increasing attention due to their broad applications in diverse fields such as the development of smart devices and sensors. Herein, a new family of AIE‐active chiral [3]rotaxanes were designed and synthesized, from which a novel CPL switching system was successfully constructed. The switching process was realized through the controlled motions of the chiral pillar[5]arene macrocycles along the axle through the addition or removal of the acetate anions, which not only modulated the chirality information transfer but also tuned the aggregations of the integrated [3]rotaxanes, thus resulting in reversible transformations between two emission states with both high photoluminescence quantum yields (PLQYs) and high dissymmetry factors (glum) values.

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Chiroptical inversion of a planar chiral redox-switchable rotaxane

Abstract: Reversible redox-switching of a planar chiral [2]rotaxane with a tetrathiafulvalene-bearing crown ether macrocycle generates a complete sign reversal of the main band in the ECD spectrum, as shown by experiment and rationalised by DFT calculations.

Cited by 58 publications

References 81 publications

Thermodynamic and electrochemical study of tailor-made crown ethers for redox-switchable (pseudo)rotaxanes

Thermodynamic and electrochemical study of tailor-made crown ethers for redox-switchable (pseudo)rotaxanes

A Multiple Chirality Switching Device for Spatial Light Modulators

AIE‐Active Chiral [3]Rotaxanes with Switchable Circularly Polarized Luminescence

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