Notizen: Ethylenedioxytetrathiafulvalenes: New Unsymmetrical π-Donors

Papavassiliou, George C.; Lagouvardos, D. J.; Kakoussis, V. C.; Mousdis, George A.

doi:10.1515/znb-1990-0819

Cited by 16 publications

(15 citation statements)

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“…Compound 9 (Figure 1) can be prepared from 1,3‐dithiol‐2‐one ( 11 ) and compound 16 37. The cross‐coupling of 11 and 16 with P(EtO) 3 in dry benzene will give a mixture of symmetrical and unsymmetrical products 35.…”

Section: Resultsmentioning

confidence: 99%

Ni Dithiolenes – A Theoretical Study on Structure–Property Relationships

et al. 2013

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The linear and nonlinear optical (L&NLO) properties, the energy difference between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO gap), the first excitation energy (E exc ), and four indices for the evaluation of the diradical character (DC) of a series of Ni dithiolene derivatives have been computed by employing density functional theory (DFT). The selected DFT functionals provide reliable results for several properties [e.g., excitation energies and (hyper)polarizabilities]. An Atoms in Molecules analysis has been performed and several related properties have been reported (e.g., the average de-[a] Institute

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Section: Resultsmentioning

confidence: 99%

Ni Dithiolenes – A Theoretical Study on Structure–Property Relationships

et al. 2013

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“…Substitution of sulfur for oxygen only concerns those chalogen atoms outer to the TTF core and had been demonstrated by the synthesis of BEDO-TTF (1) and recently EDO-TTF (2,3), the oxo analogs of BEDT-TTF (4) and EDT-TTF (5) (Scheme 1). As nicely highlighted by Zorina et al (6), BEDO-TTF salts are not isostructural with their BEDT-TTF analogs.…”

Section: Introductionmentioning

confidence: 99%

Interplay of Charge Transfer, Dimensionality, and Amide Hydrogen Bond Network Adaptability in TCNQF4 Complexes of EDO-TTF-CONH2 and EDT-TTF-CONH2

Baudron

Meźière²,

Heuzé³

et al. 2002

Journal of Solid State Chemistry

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“…The present synthesis is advantageous in view of its yield, reproducibility, and avoidance of the use of a toxic mercury reagent since the coupling partner 5 was prepared from 6 using a mercury catalyst 7,9 or from the corresponding selenone which is obtained by a more dangerous procedure using highly toxic H 2 Se. 8…”

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“…If the putative sulfur ylide C from 6 is more reactive to the cross-coupling than the self-coupling, the yield of 1 would be much improved. Thus, we examined the coupling of 4 with 1 equiv of the 2-thione 6, a synthetic precursor of the 1,3-dithiolane-2-one 5, 9 and found that the reaction gave the desired 1 in 35.2% yield. The yield was substantially increased to 56.8% when 2 equiv of 6 was used.…”

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confidence: 99%

“…In summary, sufficient amounts of the unsymmetrical donor 1 were obtained (a few grams) and its optical rotation value and spectroscopic data were obtained for the first time. The present synthesis is advantageous in view of its yield, reproducibility, and avoidance of the use of a toxic mercury reagent since the coupling partner 5 was prepared from 6 using a mercury catalyst 7,9 or from the corresponding selenone which is obtained by a more dangerous procedure using highly toxic H 2 Se. 8…”

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Efficient Synthesis of EDO-S,S-DMEDT-TTF, a Potent Organic-Donor for Synthetic Metals

Konoike¹,

Namba²,

Shinada³

et al. 2001

Synlett

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Optically active ethylenedioxy-S,S-dimethylethylenedithiotetrathiafulvalene (EDO-S,S-DMEDT-TTF: 1) has been synthesized in satisfactory yield using a triethyl phosphite-mediated cross-coupling of (5S,6S)-5,6-dimethyl-1,3-dithiolane-2-one 4 with unsubstituted 1,3-dithiolane-2-thione 6.Organic low-dimensional conductors have attracted the keen interest of both physicists and chemists for more than twenty years because of their electronic properties extending from insulators, semiconductors to metals and superconductivity. They take the form of crystalline solids and are comprised of organic donors (cation radicals) and either organic or inorganic anions. The donors of most of these are based on an extended tetrathiafulvalene (TTF) analog. 1 Namely, quasi-one-dimensional conductors are mainly associated with TTF or their derivatives of tetramethyltetraselenafulvalene (TMTSF), and quasi-two-dimensional with bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF). Both of these donors have C 2 and C s symmetry (symmetrical donors). In addition to these donors, C s symmetrical donors (unsymmetrical donor) represented by enantiomers of ethylenedioxydimethylethylenedithiotetrathiafulvalene (EDO-DMEDT-TTF (1)), a constituent of the t-type crystals which exhibit a two-dimensional metallic behavior and novel magnetic and electronic properties at low temperature, 2-4 have recently been developed. 5 Since the supply of these donors in sufficient quantities is an important subject to extend further physics studies, a number of synthetic works have been explored. The syntheses of both symmetrical and unsymmetrical donors have been performed by a one-pot triethyl phosphite-mediated coupling of 1,3-dithiolane-2-one. 6 Contrary to self-coupling providing symmetrical donors, preparation of the unsymmetrical donors requires crosscoupling between different coupling partners which inevitably incurs synthetic difficulty due to concomitant formation of symmetrical donors resulting in a decrease in the yield of the ultimate donors (vide infra). 7 In this report, we describe an efficient preparation of an unsymmetrical donor, EDO-S,S-DMEDT-TTF (1). 5,8 The reported work describes the conducting and superconducting salts based on the unsymmetrical donor 1 without detailing the complete synthetic procedure and its spectroscopic data. 8 The synthesis was performed by the coupling of (5S,6S)-5,6-dimethyl-1,3-dithiolane-2-one 4 7 with unsubstituted 1,3-dithiolane-2-one 5 8,9 using triethyl phosphite. The estimated yield of 1 was ~20%, suggesting that undesired self-coupling reactions producing symmetrical donors 2 and 3 exceeded the desired cross-coupling. We carefully examined the coupling of 4 with 1 equiv of 5, and confirmed the formation of a mixture of cross-coupling product 1 and self-coupled 2 10 and 3 11 (Scheme 1). The ratio of the products (symmetrical donors 2 and 3: unsymmetrical donor 1 = 4:1) was not identical with the theoretical ratio (Table). Despite the use of 2 equiv of 5, the yield of the desired 1 was only 12.4% and the self-coup...

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Notizen: Ethylenedioxytetrathiafulvalenes: New Unsymmetrical π-Donors

Cited by 16 publications

References 0 publications

Ni Dithiolenes – A Theoretical Study on Structure–Property Relationships

Ni Dithiolenes – A Theoretical Study on Structure–Property Relationships

Interplay of Charge Transfer, Dimensionality, and Amide Hydrogen Bond Network Adaptability in TCNQF4 Complexes of EDO-TTF-CONH2 and EDT-TTF-CONH2

Efficient Synthesis of EDO-S,S-DMEDT-TTF, a Potent Organic-Donor for Synthetic Metals

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