9242. Tetrathiafulvalene

Nomenclature

CAS number: 31366-25-3
2-(1,3-Dithiol-2-ylidene)-1,3-dithiole; Δ 2,2′-bi-1,3-dithiole; bis-1,3-dithiole; 1,4,5,8-tetrathiafulvalene; TTF.
C6H4S4; mol wt 204.36.
C 35.26%, H 1.97%, S 62.76%.

Description and references

Of interest in solid state chemistry as a conductor, catalyst or sensor due to its unusual electronic and magnetic properties. Primarily used as the parent compound for supramolecular assemblies. Prepn: F. Wudl et al., Chem. Commun. 1970, 1453. In combination with TCNQ (tetracyano-p-quinodimethane) to form first “organic metal”: J. Ferraris et al., J. Am. Chem. Soc. 95, 948 (1973); electronic structure: R. Gleiter et al., J. Electron. Spectrosc. Relat. Phenom. 2, 207 (1973). Use as a catalyst in radical reactions: R. J. Fletcher et al., J. Chem. Soc. Perkin Trans. 1 1995, 623; J. A. Murphy, S. J. Roome, ibid. 1349. TTF-mediated biosensors for glucose: T. Yu et al., J. Appl. Polym. Sci. 58, 973 (1995); for NADH: X. Zhang et al., Anal. Commun. 33, 111 (1996); for gln and glu: A. Mulchandani, A. S. Bassi, Biosens. Bioelectron. 11, 271 (1996). Review: T. Jorgensen et al., Chem. Soc. Rev. 23, 41-51 (1994). Review of electrical properties and structural data of unsymmetric TTF cmpds: J. M. Fabre et al., Synth. Met. 35, 57-64 (1990); of role in superconductors: M. R. Bryce, J. Mater. Chem. 5, 1481-1496 (1995).

Chemical structure

Properties

Orange solid in its neutral state; loses electrons to form purple cation radical and subsequent yellow dication. Also reported as yellow solid, mp 118.5-119°. Sublimes 100°, 0.3 mm. uv max (CH2Cl2): 290, 310 nm (ε 4 × 104, 4 × 104). Insol in water. Readily photo-oxidized in air to violet water-soluble radical cation. The cation is a deep purple crystalline solid, mp 155-165° (dec). uv max (H2O): 250 nm (ε 4.7 × 104); absorption max (H2O): 340, 405, 435, 575 nm (ε 4.4 × 104; 3.6 × 104; 5.6 × 104; 1.6 × 104). A counter ion is necessary to prevent further oxidation to the dication. Ethanolic solutions of the cation are stable for prolonged periods of time (>48hr).

Use

Molecular sensors; radical catalyst.