The synthesis of 4,4′(5′)-diformyltetrathiafulvalene

Andreu, Raquel; Garı́n, Javier; Orduna, Jesús; Savirón, María; Cousseau, Jack; Gorgues, A.; Morisson, V.; Nozdryn, T.; Becher, Jan; Clausen, Rasmus P.; Bryce, Martin R.; Skabara, Peter J.; Dehaen, Wim

doi:10.1016/0040-4039(94)88478-1

Cited by 47 publications

(30 citation statements)

References 23 publications

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“…The compounds 4,4'(5')-bis(hydroxymethyl)-D 2,2' -bi-1,3-dithiole [28] (7), 2-[2-(2-iodoethoxy)-ethoxy]tetrahydropyran [29] (8), 4-[bis(4-tert-butylphenyl)-(4-ethylphenyl)methyl]phenol [27] (12), compound [16] 15, a,a'-[1,4-phenylenebis(methylene)]bis(4,4'-bipyridium) bis(hexa-fluorophosphate) [30] (22¥2 PF 6 ), 2-(2-{5-[2-(2-hydroxy-ethoxy)ethoxy]naphthalen-1-yloxy}ethoxy)ethanol [25] (24), the dendritic hydrophilic stopper [11c, 26] 31 and [1,1':4',1'']terphenyl-4,4''-diol [31] (33) were all prepared according to literature procedures. Solvents were dried following methods described in the literature.…”

Section: Methodsmentioning

confidence: 99%

“…The dumbbellshaped compound 2 was obtained (Scheme 3) in 47 % yield by alkylating the phenol 21 (produced in Scheme 2), with the tosylate 14 (produced in Scheme 1) using LiBr and [18]crown-6 as catalysts in the presence of K 2 CO 3 as base. The preparation of the TTF-containing half-dumbbell compound 14 (Scheme 1) begins with alkylation of the diol [28] 7 by the iodide [29] 8 in THF using eight equivalents of NaH. Without purification, the resulting compound 9 was converted into the diol 10 by HCl-catalyzed deprotection in a MeOH/CH 2 Cl 2 solvent mixture with an overall yield of 60 % for the two steps.…”

Section: Synthesismentioning

confidence: 99%

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Redox‐Controllable Amphiphilic [2]Rotaxanes

Tseng

Vignon

Celestre

et al. 2003

Chemistry A European J

152

106

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With the fabrication of molecular electronic devices (MEDs) and the construction of nanoelectromechanical systems (NEMSs) as incentives, two constitutionally isomeric, redox-controllable [2]rotaxanes have been synthesized and characterized in solution. Therein, they both behave as near-perfect molecular switches, that is, to all intents and purposes, these two rotaxanes can be switched precisely by applying appropriate redox stimuli between two distinct chemomechanical states. Their dumbbell-shaped components are composed of polyether chains interrupted along their lengths by i) two pi-electron rich recognition sites-a tetrathiafulvalene (TTF) unit and a 1,5-dioxynaphthalene (DNP) moiety-with ii) a rigid terphenylene spacer placed between the two recognition sites, and then terminated by iii) a hydrophobic tetraarylmethane stopper at one end and a hydrophilic dendritic stopper at the other end of the dumbbells, thus conferring amphiphilicity upon these molecules. A template-directed protocol produces a means to introduce the tetracationic cyclophane, cyclobis(paraquat-p-phenylene) (CBPQT(4+)), which contains two pi-electron accepting bipyridinium units, mechanically interlocked around the dumbbell-shaped components. Both the TTF unit and the DNP moiety are potential stations for CBPQT(4+), since they can establish charge-transfer and hydrogen bonding interactions with the bipyridinium units of the cyclophane, thereby introducing bistability into the [2]rotaxanes. In both constitutional isomers, (1)H NMR and absorption spectroscopies, together with electrochemical investigations, reveal that the CBPQT(4+) ring is predominantly located on the TTF unit, leading to the existence of a single translational isomer (co-conformation) in both cases. In addition, a model [2]rotaxane, incorporating hydrophobic tetraarylmethane stoppers at both ends of its dumbbell-shaped component, has also been synthesized as a point of reference. Molecular synthetic approaches were used to construct convergently the dumbbell-shaped compounds by assembling progressively smaller building blocks in the shape of the rigid spacer, the TTF unit and the DNP moiety, and the hydrophobic and hydrophilic stoppers. The two amphiphilic bistable [2]rotaxanes are constitutional isomers in the sense that, in one constitution, the TTF unit is adjacent to the hydrophobic stopper, whereas in the other, it is next to the hydrophilic stopper. All three bistable [2]rotaxanes have been isolated as green solids. Electrospray and fast atom bombardment mass spectra support the gross structural assignments given to all three of these mechanically interlocked compounds. Their photophysical and electrochemical properties have been investigated in acetonitrile. The results obtained from these investigations confirm that, in all three [2]rotaxanes, i) the CBPQT(4+) cyclophane encircles the TTF unit, ii) the CBPQT(4+) cyclophane shuttles between the TTF and DNP stations upon electrochemical or chemical oxidation/reduction of the TTF unit, and iii) folded conformations ar...

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Section: Methodsmentioning

confidence: 99%

Section: Synthesismentioning

confidence: 99%

Redox‐Controllable Amphiphilic [2]Rotaxanes

Tseng

Vignon

Celestre

et al. 2003

Chemistry A European J

152

106

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“…[36,37] The improved synthesis of 3b was reported by González et al [11] and involves the reaction of the monolithio-TTF with N,N-dimethylacrolein to yield the transvinylogue amide according to the coupling constants in the 1 H-NMR spectra. Finally, the larger formyl-TTF vinylogue 3c was obtained by a Wittig reaction of 3b with the phosphorane 4 in a 40 % yield.…”

Section: Synthesismentioning

confidence: 99%

Tetrathiafulvalene–Polychlorotriphenylmethyl Dyads: Influence of Bridge and Open‐Shell Characteristics on Linear and Nonlinear Optical Properties

Souto

Calbo

Ratera

et al. 2017

Chemistry A European J

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Abstract:In this article, three conjugated donor-π-acceptor radical systems (1a-1c) based on a tetrathiafulvalene (TTF) unit, as electron-donor, connected to a polychlorotriphenylmethyl (PTM) radical, as electron-acceptor, through different vinylene units as bridge have been synthesized. The dependence of the intramolecular charge transfer on the length of the conjugated bridge has been analysed by different electrochemical and spectroscopic techniques. In addition, linear optical properties and the secondorder non-linear optical (NLO) response of these derivatives have been theoretically calculated by comparing with their non-radical analogues (2a-2c). Interestingly, an enhanced NLO response is predicted when the PTM is in its radical form as well as when the length of the bridge becomes longer. Theoretical calculations confirm the active role of the bridge in the electronic communication between the donor TTF and the acceptor PTM units.

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“…Cyclobis(paraquat-p-phenylene) hexafluorophosphate [33], 1-iodo-8-tetrahydropyranyloxy-3,6-dioxaoctane [64], and 4,4 0 (5 0 )-bis[methanol]tetrathia-fulvalene [65] were prepared according to literature procedures. Thin layer chromatography (TLC) was performed on silica gel 60 F 254 (E. Merck).…”

Section: General Methodsmentioning

confidence: 99%

The Power of Click Chemistry for Molecular Machines and Surface Patterning

Spruell

2011

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The synthesis of 4,4′(5′)-diformyltetrathiafulvalene

Cited by 47 publications

References 23 publications

Redox‐Controllable Amphiphilic [2]Rotaxanes

Redox‐Controllable Amphiphilic [2]Rotaxanes

Tetrathiafulvalene–Polychlorotriphenylmethyl Dyads: Influence of Bridge and Open‐Shell Characteristics on Linear and Nonlinear Optical Properties

The Power of Click Chemistry for Molecular Machines and Surface Patterning

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