A self-assembled tetrathiafulvalene box

Krykun, Serhii; Croué, Vincent; Alévêque, Olivier; Levillain, Eric; Allain, Magali; Meźière, Cécile; Carré, Vincent; Aubriet, Frédéric; Voitenko, Zoia; Goeb, Sébastien; Sallé, Marc

doi:10.1039/d0qo01543a

Cited by 5 publications

(1 citation statement)

References 82 publications

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“…[4] However, as these complexes are rather weak at room temperature, with binding constants of 6.0 and 0.6 M À 1 in CH 2 Cl 2 , for [TTF] 2 * + and [TTF * + ] 2 , respectively, [4a] their utility in supramolecular assemblies usually requires interlocking the electrophores in close proximity to each other, either via a covalent linker, by incorporation of two units inside an inclusion complex, or by incorporation of units within mechanically interlocked systems. Some selected examples include studies on mixed-valence complexes and/or π-dimers in covalently interlocked TTF oligomers, [5] inside a cucurbit [8]uril, [6] inside an electron-deficient, Pd-coordinated organic framework, [7] as units of a rigid metalla-cage, [8] within a [3]catenane, [9] and within oligorotaxanes where TTF units are part of the mechanically interlocked components. [10] Alternatively, self-association of the oxidized TTF moiety can be enforced by extending the conjugated system of TTF with a π-conjugated spacer between the two dithiole rings.…”

Section: Introductionmentioning

confidence: 99%

Dimeric Indenofluorene‐Extended Tetrathiafulvalene Motif for Enhanced Intramolecular Complexation

et al. 2021

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Tetrathiafulvalene (TTF) is a redox-active compound, which reversibly undergoes two one-electron oxidations to give stable species. Several features of TTF, such as redox and optical properties as well as geometry and self-associating nature, can be tuned by extension of the conjugated system with an aromatic linker such as an indenofluorene (IF) moiety. In this work we present the synthesis of a novel dimeric scaffold of IFextended TTF (IF-TTF) in which the units are linked by a rigid 1,4-bis(2-ethynylphenyl)buta-1,3-diyne moiety. 1 H-NMR spectroscopic studies reveal that the scaffold is highly prone to form intramolecular IF-TTF dimer complexes even in the neutral form, and stable radical cation species were formed in solution upon chemical oxidation with tris(4-bromophenyl)ammoniumyl hexachloroantimonate ('magic blue'). Electrocrystallization of the rigid scaffold yielded a semi-conducting material, which proved to be stable at ambient temperature and air.

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Section: Introductionmentioning

confidence: 99%

Dimeric Indenofluorene‐Extended Tetrathiafulvalene Motif for Enhanced Intramolecular Complexation

et al. 2021

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Stabilizing Indigo Z‐Isomer through Intramolecular Associations of Redox‐Active Appendages

et al. 2021

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In memory of Prof. Klaus HafnerPhotoswitchable small molecules, such as N,N'-disubstituted indigos, have received great interest within fields such as pharmacology, energy storage, and functional materials, as they represent key building blocks for reversible and non-invasive control of chemical processes. However, to ensure applicability of photochromic systems it is of paramount importance to manipulate the photostationary state. In this work, we achieved this by tethering two redox-active indenofluorene-extended tetrathiafulvalene units to an N,N'-disubstituted indigo photoswitch. Upon two-electron oxidation, we observe significantly enhanced stability of the Z-isomer, compared to the neutral compound, illustrated by a substantial increase in the half-life from 0.48 seconds to 22 hours. This remarkable stabilization is ascribed to formation of strong, intramolecular π-dimers between the oxidized subunits.

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Five-membered ring systems: with O and S (Se, Te) atoms

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Power

2023

Progress in Heterocyclic Chemistry

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A self-assembled tetrathiafulvalene box

Abstract: A M8L2 metalla-cage constructed through coordination-driven self-assembly from a quinonato bis-ruthenium complex and an electron-rich tetrathiafulvalene (TTF) tetrapyridyl ligand is depicted.

Cited by 5 publications

References 82 publications

Dimeric Indenofluorene‐Extended Tetrathiafulvalene Motif for Enhanced Intramolecular Complexation

Dimeric Indenofluorene‐Extended Tetrathiafulvalene Motif for Enhanced Intramolecular Complexation

Stabilizing Indigo Z‐Isomer through Intramolecular Associations of Redox‐Active Appendages

Five-membered ring systems: with O and S (Se, Te) atoms

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