Conducting Organic Radical Cation Salts with Organic and Organometallic Anions

Geiser, U.; Schlueter, John A.

doi:10.1021/cr0306844

Cited by 111 publications

(79 citation statements)

References 252 publications

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“…Their salts might thus provide new superconductive materials and/or other polymeric systems with novel properties. [66,67] It is important to mention that the parent hydrocarbons 1a, [35][36][37][38] 2a, [39,40] 3a [41] and 4a [42,43] have already been synthetized in laboratories.…”

Section: Discussionmentioning

confidence: 99%

Strong Acidity of Some Polycyclic Aromatic Compounds Annulated to a Cyclopentadiene Moiety and Their Cyano Derivatives – A Density Functional B3LYP Study

Vianello

Maksić

2005

Eur J Org Chem

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The acidity of the parent 1H‐benz[f]indene (1a), 1H‐benz[e]indene (2a), 1H‐benz[fg]acenaphthylene (3a) and 1H‐cyclopenta[l]phenanthrene (4a) and of their polycyano derivatives is examined in the gas phase and in DMSO by the DFT‐B3LYP methods. It is shown that the parent hydrocarbons exhibit modest acidities, whereas a dramatic increase in acidity is observed upon multiple cyanation leading to hyperstrong neutral organic superacids. It is found that polycyano derivatives undergo prototropic tautomerism with a consequence that the most stable tautomer contains a ketene imine C=C=NH functionality. The origin of their highly pronounced acidity is identified as a very strong anionic resonance effect efficiently assisted by a large number of CN groups in a concerted manner. It is stressed that the polycyanated anions are very stable and have a highly dispersed negative charge, which should lead to a low nucleophilicity and weak coordinating properties, thus making them potentially very useful in academic research and technological applications. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Section: Discussionmentioning

confidence: 99%

Strong Acidity of Some Polycyclic Aromatic Compounds Annulated to a Cyclopentadiene Moiety and Their Cyano Derivatives – A Density Functional B3LYP Study

Vianello

Maksić

2005

Eur J Org Chem

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“…[22] Among conducting materials, semifluorinated tetrathiafulvalene (TTF) derivatives have been prepared for Langmuir-Blodgett film formation, [23] while incorporation of highly fluorinated anions such as (CF 3 ) 3 CF(CH 2 ) 2 -SO 3 À in TTF salts also stabilized the formation of layered materials. [24,25] The very strong contrast offered by fluoroaliphatics in polymer science, biochemistry, and soft-matter chemistry let us infer that even single CF 3 groups rather than long C n F 2n + 1 perfluoroalkyl chains, adequately positioned on the rigid core, could be sufficient to provide a segregation and formation of layered crystalline structures, as very recently observed in hexafluoroacetylacetonate (hfac) complexes. [26] Indeed, the two-dimensional structures often encountered in cation radical salts are also highly desirable in the structures of the neutral TTF-like donor molecules if one is interested in the design of crystalline thin films for transistor devices.…”

Section: Introductionmentioning

confidence: 91%

Fluorine Segregation in Crystalline Materials: Structural Control and Solid‐State [2+2] Cycloaddition in CF₃‐Substituted Tetrathiafulvalene Derivatives

Jeannin

Fourmigué

2006

Chemistry A European J

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The well-known influence of long perfluorinated chains on the structures and stability of amphiphilic molecules in liquid crystalline mesophases or mesoscopic micellar arrangements is evaluated here in the realm of crystalline materials based on rigid aromatic molecules bearing only a limited number of CF(3) moieties. Tetrathiafulvalene (TTF) derivatives bearing one or two CF(3) groups, that is, (Z)- and (E)-(CF(3))(2)TTF ((Z)-1, (E)-1), EDT-TTF-CF(3) (2), and EDT-TTF(CF(3))(2) (3) (EDT=ethylenedithio) are prepared from the 1,3-dipolar reaction of methyl 4,4,4-trifluorotetrolate with ethylenetrithiocarbonate. The structures of neutral (Z)-1, (E)-1, 2, and 3 as indicated by single-crystal X-ray diffraction measurements reveal the recurrent formation of layered structures with a strong segregation of the fluorinated moieties and formation of fluorous bilayers, attributed to the amphiphilic character of those TTF derivatives upon CF(3) functionalization, and without need for longer C(n)F(2n+1) (n>1) perfluorinated chains. The short intermolecular distance between outer C==C double bonds observed in the layered structure of (E)-1 allows a solid-state [2+2] photocyclization with formation of chiral dyads incorporating the characteristic cyclobutane ring. These dyads containing two dihydrotetrathiafulvalene moieties facing each other exhibit reversible oxidation to the mixed-valence radical cation state and organize in the solid-state into the same layered structures with fluorous bilayers.

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“…Since then, a * Corresponding author: hashimoto@imr.tohoku.ac.jp number of TTF and TCNQ derivatives were designed as donor and acceptor molecules [5]. Among them, TMTTF (tetramethyltetrathiafulvalene) is a representative donor molecule, which forms quasi-one-dimensional (quasi-1D) charge-transfer salts (TMTTF) 2 X, where X is a monovalent anion [4].…”

Section: Introductionmentioning

confidence: 99%

“…1(a)] [5,12]. Although the HOMO dis- tribution of the BPDT-TTF molecule is similar to that of the BEDT-TTF molecule [see Fig.…”

Section: Introductionmentioning

confidence: 99%

Dimer-Mott and charge-ordered insulating states in the quasi-one-dimensional organic conductors δP′ - and δC′−(BPDT-TTF)
Kobayashi
¹
,
Hashimoto
²
,
Yoneyama
³

et al. 2017
Phys. Rev. B
3
0
1
0
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Conducting Organic Radical Cation Salts with Organic and Organometallic Anions

Cited by 111 publications

References 252 publications

Strong Acidity of Some Polycyclic Aromatic Compounds Annulated to a Cyclopentadiene Moiety and Their Cyano Derivatives – A Density Functional B3LYP Study

Strong Acidity of Some Polycyclic Aromatic Compounds Annulated to a Cyclopentadiene Moiety and Their Cyano Derivatives – A Density Functional B3LYP Study

Fluorine Segregation in Crystalline Materials: Structural Control and Solid‐State [2+2] Cycloaddition in CF₃‐Substituted Tetrathiafulvalene Derivatives

Dimer-Mott and charge-ordered insulating states in the quasi-one-dimensional organic conductors δP′ - and δC′−(BPDT-TTF)
Kobayashi
¹
,
Hashimoto
²
,
Yoneyama
³

et al. 2017
Phys. Rev. B
3
0
1
0
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Conducting Organic Radical Cation Salts with Organic and Organometallic Anions

Cited by 111 publications

References 252 publications

Strong Acidity of Some Polycyclic Aromatic Compounds Annulated to a Cyclopentadiene Moiety and Their Cyano Derivatives – A Density Functional B3LYP Study

Strong Acidity of Some Polycyclic Aromatic Compounds Annulated to a Cyclopentadiene Moiety and Their Cyano Derivatives – A Density Functional B3LYP Study

Fluorine Segregation in Crystalline Materials: Structural Control and Solid‐State [2+2] Cycloaddition in CF3‐Substituted Tetrathiafulvalene Derivatives

Dimer-Mott and charge-ordered insulating states in the quasi-one-dimensional organic conductors δP′ - and δC′−(BPDT-TTF)Kobayashi1, Hashimoto2, Yoneyama3 et al. 2017Phys. Rev. B3010View full textAdd to dashboardCite

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Fluorine Segregation in Crystalline Materials: Structural Control and Solid‐State [2+2] Cycloaddition in CF₃‐Substituted Tetrathiafulvalene Derivatives

Dimer-Mott and charge-ordered insulating states in the quasi-one-dimensional organic conductors δP′ - and δC′−(BPDT-TTF)
Kobayashi
¹
,
Hashimoto
²
,
Yoneyama
³

et al. 2017
Phys. Rev. B
3
0
1
0
View full text Add to dashboard Cite