Functionalised Trimethyltetrathiafulvalene (TriMe-TTF) Derivatives via Reactions of Trimethyltetrathiafulvalenyllithium with Electrophiles: X-ray Crystal Structures of Benzoyl-TriMe-TTF and Benzoylthio-TriMe-TTF

Moore, Adrian J.; Batsanov, Andrei S.; Cole, Jason C.; Howard, Judith A. K.

doi:10.1055/s-1995-3972

Cited by 47 publications

(49 citation statements)

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“…For compound 43, this band appeared at significantly higher energies (l max = 382 nm) since the S±C=C±C=O conjugation was reduced due to intramolecular steric effects: the larger N,N-dimethylamide substituent is rotated out of the TTF plane. A similar mesomeric effect on the bond lengths has been observed in the crystal structures of trimethyl-TTF derivatives 45 [59] and 46. [60] The extent of this conjugative effect is clearly seen in a comparison of benzoyl and S-benzoyl analogues 45 and 47, both in solution and in the solid state.…”

Section: Mesomerically Conjugated Carbonyl Thiocarbonyl Ester and supporting

confidence: 71%

“…[60] The extent of this conjugative effect is clearly seen in a comparison of benzoyl and S-benzoyl analogues 45 and 47, both in solution and in the solid state. [59] The former is dark purple with an ICT band at l max = 500 nm in acetonitrile, whereas the latter is orange, and the lowest energy absorption is at l max = 374 nm in acetonitrile. Both redox waves are anodically shifted in 45 compared to 47 (DE 1 1/2 = 50 mV, DE 2 1/2 = 90 mV).…”

Section: Mesomerically Conjugated Carbonyl Thiocarbonyl Ester and mentioning

confidence: 99%

“…The X-ray structure of compound 45, and the crystallographic numbering scheme, is shown in Figure 9. [59] There are dimers of weakly interacting, inversion-related molecules; there are no significant close intermolecular contacts, allowing a clear interpretation of the bond lengths in terms of intramolecular interactions. The shortest intradimer contact is C(1)_C(1¢) = 3.49 ; the phenyl ring is substantially out of the plane of the TTF system, inhibiting the formation of molecular stacks.…”

Section: Mesomerically Conjugated Carbonyl Thiocarbonyl Ester and mentioning

confidence: 99%

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Tetrathiafulvalenes as π-Electron Donors for Intramolecular Charge-Transfer Materials

Bryce

1999

Adv. Mater.

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333

144

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Although tetrathiafulvalene (TTF) and its derivatives have been extensively studied for more than 25 years as p-electron donors in intermolecular charge-transfer materials, the intriguing potential of TTF as a donor in an intramolecular sense has only recently been developed. Many versatile, functionalized TTF building blocks are now readily available, and this article will review a range of compounds in which TTF is covalently linked to an electron acceptor moiety by a variety of linking units, sometimes giving rise to an intramolecular charge-transfer (ICT) interaction, which is most frequently manifested in the optical and electrochemical properties. In this context, acceptor subunits include: tetracyano-p-quinodimethane, quinones, electrondeficient aryl groups, pyridinium and bipyridinium units, fullerenes, phthalocyanines, and mesomerically conjugated carbonyl, thiocarbonyl, ester, and related groups. This work paves the way for more systematic and detailed studies of TTF±spacer±A molecules (where A is an acceptor) in which there is increased control of the structural, electronic, optical, and magnetic properties arising from ICT interactions in the ground state, or in the excited state.

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Section: Mesomerically Conjugated Carbonyl Thiocarbonyl Ester and supporting

confidence: 71%

Section: Mesomerically Conjugated Carbonyl Thiocarbonyl Ester and mentioning

confidence: 99%

Section: Mesomerically Conjugated Carbonyl Thiocarbonyl Ester and mentioning

confidence: 99%

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Tetrathiafulvalenes as π-Electron Donors for Intramolecular Charge-Transfer Materials

Bryce

1999

Adv. Mater.

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333

144

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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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“…The synthesis of these electron donors was carried out using a palladium-catalyzed double cross-coupling reaction involving various dibromothiophene or bithiophene (1 equiv) and the tributylstannyltrimethyltetrathiafulvalene (tMeTTF-SnBu3) (2 equiv). The latter was previously synthesized in 79% yield [14] by using lithiation of trimethyltetrathiafulvalene (tMeTTF) [15] followed by treatment with tributyltin chloride.…”

Section: Chemistrymentioning

confidence: 99%

Computational study of the chemical reactivity properties of bis (trimethyl tetrathiafulvalenyl) thiophene

Bendjeddou

Abbaz

Gouasmia

et al. 2017

JAC

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The chemical reactivity of four bis (trimethyltetrathiafulvalenyl) thiophene is determined by its potential (electronic) energy (hyper) surface. All the quantum chemical calculations have been carried out using DFT level of theory, B3LYP functional and 6-31G(d,p) as basis set. Molecular electrostatic potential (MEP) and HOMO-LUMO energy levels have been performed. The local reactivity descriptor such as Fukui function is also performed to determine the reactive sites within the title molecules. The chemometric methods PCA and HCA were employed to find the subset of variables that could correctly classify the compounds according to their reactivity.

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Functionalised Trimethyltetrathiafulvalene (TriMe-TTF) Derivatives via Reactions of Trimethyltetrathiafulvalenyllithium with Electrophiles: X-ray Crystal Structures of Benzoyl-TriMe-TTF and Benzoylthio-TriMe-TTF

Cited by 47 publications

References 0 publications

Tetrathiafulvalenes as π-Electron Donors for Intramolecular Charge-Transfer Materials

Tetrathiafulvalenes as π-Electron Donors for Intramolecular Charge-Transfer Materials

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

Computational study of the chemical reactivity properties of bis (trimethyl tetrathiafulvalenyl) thiophene

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