Highly conjugated π-electron donors for organic metals: synthesis and redox chemistry of new 1,3-dithiole and 1,3-selenathiole derivatives

Moore, Adrian J.

doi:10.1039/p19910000157

Cited by 117 publications

(75 citation statements)

References 54 publications

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“…2-Iodo-9,10-bis(4,5-dimethyl-1,3-dithiol-2-ylidene)-9,10-dihydroanthracene (9) was prepared by the Wittig-Horner reaction by condensation of the 2-iodoanthraquinone (7) with the carbanion generated from dimethyl (4,5-dimethyl-1,3-dithiol-2-yl)phosphonate (8) and butyllithium. [48][49][50] The resulting iodo-substituted extended TTF 9 was finally grafted onto 6 in the last Sonogashira cross-coupling reaction to afford the first triad T1 in a yield of 63 % after purification.…”

Section: Resultsmentioning

confidence: 99%

Hole‐Transfer Dyads and Triads Based on Perylene Monoimide, Quaterthiophene, and Extended Tetrathiafulvalene

Boixel

Blart

Pellegrin

et al. 2010

Chemistry A European J

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Two families of dyad and triad systems based on perylene monoimide (PMI), quaterthiophene (QT), and 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene (extended tetrathiafulvalene, exTTF) molecular components have been designed and synthesized. The dyads (D1 and D2) are of the PMI-QT type and the triads (T1 and T2) of the PMI-QT-exTTF type. The two families differ in the saturated or unsaturated nature of the linker groups (ethynylene in D1 and T1, ethylene in D2 and T2) that bridge the molecular components. The dyads and triads have been characterized by electrochemical, photophysical, and computational methods. Both the experimental and the computational (DFT) results indicate that in the unsaturated systems strong intercomponent interactions lead to substantial perturbation of the properties of the subunits. In particular, in T1, delocalization is particularly effective between the QT and exTTF units, which would be better viewed combined as a single electronic subsystem. For the dyad systems, the photophysics observed following excitation of the PMI unit is solvent-dependent. In moderately polar solvents (dichloromethane, diethyl ether) fast charge separation is followed by recombination to the ground state. In toluene, slow conversion to the charge-separated state is followed by intersystem crossing and recombination to yield the triplet state of the PMI unit. The behavior of the triads, on the other hand, is remarkably similar to that of the corresponding dyads, which indicates that, after primary charge separation, hole shift from the oxidized QT component to exTTF is quite inefficient. This unexpected result has been rationalized on the basis of the anomalous (simultaneous two-electron oxidation) electrochemistry of exTTF and with the help of DFT calculations. In fact, although exTTF is electrochemically easier to oxidize than QT by around 0.6 V, the one-electron redox orbitals (HOMOs) of the two units in triad T2 are almost degenerate.

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Section: Resultsmentioning

confidence: 99%

Hole‐Transfer Dyads and Triads Based on Perylene Monoimide, Quaterthiophene, and Extended Tetrathiafulvalene

Boixel

Blart

Pellegrin

et al. 2010

Chemistry A European J

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“…[9] By analogy with the preparation of 3 by monolithiation of compound 2 with lithium diisopropylamide (LDA), followed by in situ trapping with methylchloroformate, [19,20] we have explored the possibility of difunctionalising analogue 8 (which is readily available in ca. 1 g batches) [7] using Scheme 2. Synthesis of 9؊11 the same protocol.…”

Section: Scheme 1 Synthesis Of 4؊7mentioning

confidence: 99%

“…In this context our attention is focussed on 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene (1) [7] and derivatives (e.g. 2 and 3 [19,20] ) which undergo a single, quasi-reversible, two-electron oxidation wave to yield a thermodynamically stable dication at E ox ഠ ϩ0.3 to ϩ0.4 V (in MeCN vs. Ag/AgCl) in the cyclic voltammogram.…”

Section: Introductionmentioning

confidence: 99%

Hydroxymethyl-Functionalised 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-Dihydroanthracene π-Electron Donors as Synthetic Intermediates for Supramolecular Structures

et al. 2001

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The synthesis of new derivatives of 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene is reported. 1 H NMR studies on compound 4 are consistent with two conformers of the saddle-shaped molecule which interconvert by a boat−boat flipping of the central ring at high temperature. The hydroxymethyl substituent of 4 is readily esterified to yield the benzoyl and 2-naphthaloyl ester derivatives 5a and 5b, respectively, and the dimer and the trimer structures 6 and 7, respectively, by reaction with benzoyl chloride, 2-naphthaloyl chloride, 1,4-benzenedicarbonyl chloride and 1,3,5-benzenetricarbonyl chloride. Deprotonation of 9-(4,5-dimethyl-1,3-dithiol-2-ylidene)-10-(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene (8) using lithium bis(trimethylsilyl) amide (LHMDS) followed by in situ quenching of the lithiated intermediate with methylchloroformate gave the diester derivative 10 (96% yield), whereas using LDA gave the monoester

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“…[18] The reaction of 4 with phosphorus oxychloride in N,N-dimethylformamide (DMF) gave compound 5 in 58 % yield. Reaction of 5 with the anion generated from phosphonate ester reagents 6 [19] and 7 [20] under Horner-Wadsworth-Emmons conditions gave the 1,3-dithiol-2-ylidene derivatives 8 and 11, respectively, as red solids in approximately 60 % yields. By analogy with the preparation of 5, compound 9 was obtained from 8 in 95 % yield.…”

Section: Resultsmentioning

confidence: 98%

Remarkable Interplay of Redox States and Conformational Changes in a Sterically Crowded, Cross‐Conjugated Tetrathiafulvalene Vinylog

Amriou¹,

Perepichka²,

Batsanov³

et al. 2006

Chemistry A European J

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Derivatives of 9-[2-(1,3-dithiol-2-ylidene)ethylidene]thioxanthene have been synthesized using Horner-Wadsworth-Emmons reactions of (1,3-dithiol-2-yl)phosphonate reagents with thioxanthen-9-ylidene-acetaldehyde (5). Further reactions lead to the sterically crowded cross-conjugated "vinylogous tetrathiafulvalene" derivative 9-[2,3-bis-(4,5-dimethyl-1,3-dithiol-2-ylidene)-propylidene]thioxanthene (10). X-ray crystallography, solution electrochemistry, optical spectroscopy, spectroelectrochemistry, and simultaneous electrochemistry and electron paramagnetic resonance spectroscopy, combined with theoretical calculations performed at the B3LYP/6-31G(d) level, elucidate the interplay of the electronic and structural properties in these molecules. For compound 10, multistage redox behavior is observed: the overall electrochemical process can be represented by 10-->10(.+)-->10(2+)-->10(4+) with good reversibility for the 10-->10(.+)-->10(2+) transformations. At the tetracation stage there is the maximum gain in aromaticity at the dithiolium and thioxanthenium rings. Theory predicts that for 10, 10(.+), and 10(2+) the trans isomers are more stable than the cis isomers (by ca. 2-18 kJ mol(-1)), whereas for 10(4+) the cis isomer becomes more stable than the trans isomer (by ca. 25 kJ mol(-1)) [trans and cis refer to the arrangement of the two dithiole moieties with respect to the central ==C(R)--C(H)== fragment]. These data explain the detection in cyclic voltammograms of both trans and cis isomers of 10 and 10(.+) during the reduction of 10(4+) at fast scan rates (>100 mV s(-1)) when the cis-trans isomerization is not completed within the timescale of the experiment. The X-ray structure of the charge-transfer complex (CTC) of 10 with 2,4,5,7-tetranitrofluorene-9-dicyanomethylenefluorene (DTeF) [stoichiometry: 10(.+)(DTeF)(2) (.-)2 PhCl] reveals a twisted conformation of 10(.+) (driven by the bulky thioxanthene moiety) and provides a very rare example of segregated stacking of a fluorene acceptor in a CTC.

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Highly conjugated π-electron donors for organic metals: synthesis and redox chemistry of new 1,3-dithiole and 1,3-selenathiole derivatives

Cited by 117 publications

References 54 publications

Hole‐Transfer Dyads and Triads Based on Perylene Monoimide, Quaterthiophene, and Extended Tetrathiafulvalene

Hole‐Transfer Dyads and Triads Based on Perylene Monoimide, Quaterthiophene, and Extended Tetrathiafulvalene

Hydroxymethyl-Functionalised 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-Dihydroanthracene π-Electron Donors as Synthetic Intermediates for Supramolecular Structures

Remarkable Interplay of Redox States and Conformational Changes in a Sterically Crowded, Cross‐Conjugated Tetrathiafulvalene Vinylog

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