Radical-cation salts based on TTF(s)–DHTTF (dihydrotetrathiafulvalene) fused donors: electrical conductivities and crystal structure

Abstract

The electrochemical properties of TTF(s)-DHTTF fused donors, the electrical conductivities of their radical-cation salts, and the crystal structure of (3)2Au12 are described.

New Trends in the Synthesis of π-Electron Donors for Molecular Conductors and Superconductors

“…For synthesis of the parent TTF-DHTTF donor DTDH-TTP, demethoxycarbonylation of 9, prepared by the (MeO) 3 P-mediated coupling of 7a and thione 8b in 82% yield, by using LiBr‚H 2 O in HMPA was employed (40% yield). 15 The yield of the product in the Me 3 Al-promoted reaction is sometimes improved by alternating the order of addition in the experiment, 10c i.e., a tin dichalcogenolate is first reacted with Me 3 Al, and then an ester is added. In this case, it is likely that the Sn/Al transmetalation occurs and the resulting bis-(dimethylaluminum) dichalcogenolate reacts with the ester.…”

“…The cis stereochemistry for the fusion pattern of the dichalcogenane ring in 14a or 14b was secured by X-ray crystallographic analysis. 15 Oxidation of the tetrathioethane moiety of 14b was carried out by reaction with DDQ, affording the dihydrodithiin-fused oxone 15 in 60% yield. Oxones 14b and 15 could be converted into tin dithiolates 16 and 17.…”

Highly Functionalized Tetrathiafulvalenes: Riding along the Synthetic Trail from Electrophilic Alkynes

“…This methodology has also been applied to extended analogues of TTF or TSeF by the group of Yoshida 92a (the dienic 38 92b,c,93b or trienic 39 93a,b vinylogues, dendralenes,93c and radialenes,93d) or to fused-TTF derivatives by Misaki et al (BDT-TTP 40 , DT-TTFs 41 , DTEDT 42 , its selenium analogue 43 97 ) or by Yamada et al (DTH-TTP 44 ,) but also by Frère et al to hybrid TTF analogues 45 using oligo furan or thiophene-2,5-diylvinylenes as π-conjugated spacers, Chart 2 …”

Synthesis Strategies and Chemistry of Nonsymmetrically Substituted Tetrachalcogenafulvalenes

“…Besides the synthesis of numerous nonsymmetric TTFs, this method has also been extended successfully to the synthesis of original donors containing the tetrathiapentalene (TTP) unit and to the preparation of new fused bis-TTFs (Scheme ) that lead to a series of materials exhibiting very high electrical conductivity. ,

39

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“…The Besides the synthesis of numerous nonsymmetric TTFs, this method has also been extended successfully to the synthesis of original donors containing the tetrathiapentalene (TTP) unit and to the preparation of new fused bis-TTFs (Scheme 39) that lead to a series of materials exhibiting very high electrical conductivity. 194,195 The thiapendione (39.1), generally used as starting compound, provides the partially selenium-containing derivative 39.4 via an organometallic coupling reaction. This is then converted into the fused-TTF 39.6 by the one/thione (39.4/39.5) cross-coupling Disadvantages and Advantages.…”