Heteroatom Bridged Tetrathiafulvalenes

Avarvari, Narcis

doi:10.1002/ejic.202000207

Cited by 8 publications

(7 citation statements)

References 67 publications

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“…In such compounds, the TTF core can be reversibly oxidized to give a monocationic species. The unique electronic properties of TTF are also reflected in phosphorus-functionalized TTF derivatives like the bis(tetrathiafulvalene) derivative III , fused by a middle 1,4-dihydro-1,4-diphosphinine moiety, reported by Avarvari and Fourmigué . For instance, after single oxidation of III , the resulting radical is delocalized over the entire molecule, which was proven by electron paramagnetic resonance spectroscopy.…”

Section: Introductionmentioning

confidence: 86%

Toward a 1,4-Diphosphinine-Based Molecular CPS-Ternary Compound

et al. 2021

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Synthesis of the tricyclic 1,3-dithiole-2-thione-derived 1,4-dihydro-1,4-diphosphinine is presented using a base-induced ring formation protocol and chloro(diethylamino)(1,3-dithiole-2-thion-4-yl)phosphane as the starting point. P-oxidation reactions of dihydrodiphosphinine by chalcogens led to bis(P-oxide), bis(P-sulfide), or bis(P-selenide), respectively; all tricyclic compounds were obtained as cis/trans mixtures. 1,4-Dihydro-1,4-diphosphinine was converted into 1,4-dichloro-1,4-dihydro-1,4-diphosphinine. This compound is almost insoluble in organic solvents, furnished selectively the trans-bis(amino) derivative upon a 2-fold P-substitution reaction with the weak nucleophile potassium bis(trimethylsilyl)amide, and reacted also with alcohols ROH (R = nBu, iPr, tBu) to give cis/trans mixtures of the corresponding bis(alkoxy) derivatives. Furthermore, the dichloro derivative could be reduced to a 1,4-diphosphinine using PnBu3, but, unfortunately, the stubbornly insoluble product could be neither purified nor crystallized. Despite this, we achieved a thermal [4 + 2] cycloaddition reaction of this first CPS-ternary compound with diethylacetylene dicarboxylate to obtain the corresponding diphosphabarrelene, thus providing indirect evidence for the aromatic tricyclic diphosphinine. Detailed density functional theory studies on the formation of 1,4-diphosphinine provided insights into formation pathways as well as NMR, IR, and UV/vis data.

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Section: Introductionmentioning

confidence: 86%

Toward a 1,4-Diphosphinine-Based Molecular CPS-Ternary Compound

et al. 2021

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“…One way of modification of TTF is the preparation of bridged TTF molecules, in which the TTF units are linked by one or more spacer groups. 10 These electron-donor systems can possess electronic communication between the redox-active TTF units. Depending on the nature of the linkage, this communication can be promoted by through-bond or through-space interactions or even shut down to achieve mixed valence states.…”

Section: Introductionmentioning

confidence: 99%

“…Depending on the nature of the linkage, this communication can be promoted by through-bond or through-space interactions or even shut down to achieve mixed valence states. 10 Different main group elements have been used to link two TTF units, and the bridging heteroatoms determine the orientation and degree of interaction between the TTF units. Most of these derivatives are of the X(TTF) 2 type in which X stands for S, 11 Se, 11 Te, 12 SiMe 2 , 8 c PPh 8 c and Hg.…”

Section: Introductionmentioning

confidence: 99%

Access to and reactions of P-functional 1,4-dihydro-1,4-diphosphinines fused to two TTF units

Kermanshahian¹,

Kalisch²,

Kelemen³

et al. 2023

Dalton Trans.

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“…Therefore, we have decided to simply connect these components by covalent bonds to construct an electrically neutral but partially oxidized TTF +0.5 –X – –TTF +0.5 triad molecule. On the basis of this strategy, we have designed {[(R 2 -TTF-Cat) 2 ] + B – } • (Figure , bottom) by using a boron anion B – as the linker X – to bridge two partially oxidized TTF +0.5 skeletons through catechol moieties (=Cat) . It should be noted although the electrical charges are canceled within the molecule, one unpaired electron derived from the two TTF +0.5 skeletons (formally corresponding to the [(TTF) 2 ] •+ state) should exist on this molecule; thus, this molecule is expected to be a purely organic zwitterionic neutral radical having partially oxidized π-electron moieties …”

Section: Introductionmentioning

confidence: 99%

Partially Oxidized Purely Organic Zwitterionic Neutral Radical Conductor: Multi-step Phase Transitions and Crossover Caused by Intra- and Intermolecular Electronic Interactions

et al. 2022

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Formation of a partially charge-transfer or partially oxidized/reduced state has been one of the most important requirements for the development of highly conducting molecular materials, such as organic metals and superconductors. This requirement has been fulfilled by combining appropriate electron-donor and acceptor molecules to construct multi-component molecular complexes/salts, such as (TTF+0.59)(TCNQ–0.59) and (BEDT-TTF+0.5)2X–, where TTF = tetrathiafulvalene, TCNQ = tetracyanoquinodimethane, BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene, and X = monovalent inorganic anion. Here, we propose a methodology to fulfill this requirement by a single neutral molecule; namely, we have connected two TTF+0.5-type partially oxidized π-skeletons through a boron anion to design a purely organic zwitterionic neutral radical {[(PDT-TTF-Cat) 2 ] + B – } • . This molecule was successfully obtained as air-stable crystals containing solvent tetrahydrofuran (THF) molecules. Measurements of electrical resistivity, magnetic susceptibility, and X-ray diffraction reveal that the partially oxidized state is certainly formed, which enables realization of a 3/4-filled electron band. Furthermore, this system has intramolecular charge degrees of freedom, attributable to the two TTF+0.5 π-skeletons introduced into the molecule. The resulting interplay of intra- and intermolecular charge degrees of freedom (or simply, intra- and intermolecular electronic interactions) has led to multi-step phase transitions and crossover, providing unique strongly correlated electron properties, such as the formation of a three-dimensional charge-ordered dimer-Mott insulating state and its melting triggered by disorder–order transformation of the co-crystallized solvent THF molecules at low temperatures.

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Heteroatom Bridged Tetrathiafulvalenes

Cited by 8 publications

References 67 publications

Toward a 1,4-Diphosphinine-Based Molecular CPS-Ternary Compound

Toward a 1,4-Diphosphinine-Based Molecular CPS-Ternary Compound

Access to and reactions of P-functional 1,4-dihydro-1,4-diphosphinines fused to two TTF units

Partially Oxidized Purely Organic Zwitterionic Neutral Radical Conductor: Multi-step Phase Transitions and Crossover Caused by Intra- and Intermolecular Electronic Interactions

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