Crown-annelated tetrathiafulvalenes: synthesis of new functionalised derivatives and spectroscopic and electrochemical studies of metal complexation

Dieing, Reinhold; Morisson, V.; Moore, Adrian J.; Goldenberg, Leonid M.; Raoul, Jean-Michel; Petty, Michael C.; Garı́n, Javier; Savirón, María; Lednev, Igor K.; Hester, R. E.; Moore, John N.

doi:10.1039/p29960001587

Cited by 27 publications

(16 citation statements)

References 40 publications

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“…[7,9] For SAMs of compounds 6a, 6b, and 9 the CV response to metal cations in acetonitrile was similar to the solution result. [7,9] For SAMs of compounds 6a, 6b, and 9 the CV response to metal cations in acetonitrile was similar to the solution result.…”

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confidence: 64%

“…The key starting reagent in our syntheses of compounds 6 and 9 (Scheme 1) is compound 3, [9] the hydrolysis of which under basic conditions (1 M sodium hydroxide in dioxane) yielded, after acidic work-up, the acid derivative 4 (75 % yield). Treatment of acid 4 with either 12-bromo-1dodecanol or 6-bromo-1-hexanol in the presence of dicyclohexylcarbodiimide (DCC) and N,N-dimethylaminopyridine (DMAP) afforded ester derivatives 5a and 5b, respectively (75 and 85 % yield, respectively) with subsequent conversion of the bromide into a thiol being achieved by treatment with thiourea followed by basic hydrolysis of the intermediate isothiouronium salt to afford the target derivatives 6a and 6b (42 and 33 % yield, respectively).…”

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confidence: 99%

“…compounds 2, which have similar ester substituents and also exhibited no CV response in water). The equilibrium constant for Ag + binding in solution was estimated from electrochemical data using published procedures [9] as log K obs = 2.0±2.5. [19] Electrochemical recognition for compounds 6a, 6b, and 9 has been studied in solution and as SAMs in the presence of different metal cations.…”

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confidence: 99%

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Cation Recognition by Self-Assembled Layers of Novel Crown-Annelated Tetrathiafulvalenes

Moore¹,

Goldenberg

Petty

et al. 1998

Adv. Mater.

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The combination of molecular recognition [1] and selfassembly processes [2] offers a powerful route to the development of nanoscale systems that have technological applications as sensors, devices, and switches. [3] Macrocyclic ligands continue to attract widespread attention, [4] especially when complexation of a neutral or ionic guest at one site in the molecule induces a change in the optical [5] or redox properties [6] of the system.The recent incorporation of the electroactive tetrathiafulvalene (TTF) unit into metal-binding macrocyclic structures has demonstrated that they can function as metal-cation sensors in organic media. [7] The presence of a metal cation imposes an inductive effect on the polarizable TTF system, resulting in an anodic shift of the first oxidation potential as indicated by cyclic voltammetry experiments (e.g., for compound 1, a maximum shift of DE 1,1/2 = 80 mV for Na + complexation has been observed); [7] the second oxidation potential is essentially unchanged, consistent with the expulsion of the metal cation after the first oxidation. There is current interest in electrochemically active self-assembled monolayers (SAMs), [8] and the recent observation of stable redox chemistry of TTF derivatives 2 in self-assembled monolayers [8b] prompted us to investigate thin-film electrochemical sensors based on the cation-sensitive redox-active molecules 6 and 9 immobilized on a metal surface. SAMs represent an attractive method for device fabrication, having the advantages of straightforward preparation and being generally very robust (stable to solvents, acids, and bases). The key starting reagent in our syntheses of compounds 6 and 9 (Scheme 1) is compound 3, [9] the hydrolysis of which under basic conditions (1 M sodium hydroxide in dioxane) yielded, after acidic work-up, the acid derivative 4 (75 % yield). Treatment of acid 4 with either 12-bromo-1-dodecanol or 6-bromo-1-hexanol in the presence of dicyclohexylcarbodiimide (DCC) and N,N-dimethylaminopyridine (DMAP) afforded ester derivatives 5a and 5b, respectively (75 and 85 % yield, respectively) with subsequent conversion of the bromide into a thiol being achieved by treatment with thiourea followed by basic hydrolysis of the intermediate isothiouronium salt to afford the target derivatives 6a and 6b (42 and 33 % yield, respectively). In both cases, this last step gave a complex reaction mixture; consequently, the purified yields for compounds 6a and 6b were reduced as a result of repeated chromatography. The byproducts could not be obtained pure and their structures are unknown. Reduction of compound 3 to afford the methanol derivative 7 occurred in dichloromethane at ±78 C using diisobutylaluminum hydride (DIBAL-H) [10] (85 % yield). Using a modification [11] of the Mitsunobu reaction [12] we successfully converted alcohol 7 into sulfanylmethyl derivative 9:[13] a mixture of compound 7 and thioacetic acid in tetrahydrofuran was added to a stirred mixture of diisopropyl azodicarboxylate (DIAD) and triphenylphosphine in tetrahydrofur...

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Cation Recognition by Self-Assembled Layers of Novel Crown-Annelated Tetrathiafulvalenes

Moore¹,

Goldenberg

Petty

et al. 1998

Adv. Mater.

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“…Interestingly, the E $\rm{_{1}^{ox}}$ shifts reach a limit when approximately stoichiometric amounts of Sr 2+ or Pb 2+ (or Ba 2+ ) are added to receptors 2 (or 3 ). This result provides further evidence for the high stability of the 1:1 complexes and is in marked contrast to observations previously made on crown ether TTF derivatives for which a 250‐fold excess of added metallic cation was necessary to get saturation of the system 3a, 3b…”

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Tetrathiafulvalene Crowns: Redox-Switchable Ligands

et al. 2001

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A series of redox-responsive ligands that associate the electroactive tetrathiafulvalene core with polyether subunits of various lengths has been synthesized. X-ray structures are provided for each of the free ligands. The requisite structural criteria for reaching switchable ligands are satisfied for the largest macrocycles, that is, planarity of the 1,1',3,3'-tetrathiafulvalene (TTF) pi system and correctly oriented coordinating atoms. The ability of these ligands to recognize various metal cations as a function of the cavity size has been investigated by various techniques (LSIMS, 1H NMR, and UV/Vis spectroscopy, cyclic voltammetry). These systems exhibit an unprecedented high coordination ability among TTF crown ethers. Their switchable ligating properties have been confirmed by cyclic voltammetry, and metal-cation complexation has been illustrated by X-ray structures of three of the corresponding metal complexes (Pb2+, Sr2+, and Ba2+). Solid-state structures of these complexes display original packing modes with channel-like arrangements.

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“…Cation binding in 3 has also been monitored by UV±vis spectroscopy. 18 Fig. 1 shows that complexation of Ag z , Na z and Ba 2z results in a speci®c change in the electronic absorption spectrum of the TTF chromophore: the spectra of non-complexed and fully-complexed forms are shown.…”

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Functionalised tetrathiafulvalenes: new applications as versatile π‐electron systems in materials chemistry

2000

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Not only a component of molecular conductors! Tetrathiafulvalene (TTF) and its derivatives are versatile building blocks in many areas of materials chemistry. This article reviews the current role of substituted TTFs in cation sensors, liquid crystals, intramolecular chargetransfer and nonlinear optical materials, supramolecular switches and devices, and redox polymers (main-chain, side-chain and dendritic systems).

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Crown-annelated tetrathiafulvalenes: synthesis of new functionalised derivatives and spectroscopic and electrochemical studies of metal complexation

Cited by 27 publications

References 40 publications

Cation Recognition by Self-Assembled Layers of Novel Crown-Annelated Tetrathiafulvalenes

Cation Recognition by Self-Assembled Layers of Novel Crown-Annelated Tetrathiafulvalenes

Tetrathiafulvalene Crowns: Redox-Switchable Ligands

Functionalised tetrathiafulvalenes: new applications as versatile π‐electron systems in materials chemistry

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