ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Extremely Expanded Tetrathiafulvalenes with Polyene Spacers. Carotinoid Tetrathiafulvalenes. Polymethin-Tetracyanotetrathiafulvalene Radical Cations, a New Class of ViolenesThe synthesis of extended tetrathiafulvalenes 11 with di-, tetra-, hexa-, octa-, deca- and dodecamethine spacers is described by a PPh3-induced Wittig-reaction-like condensation of the corresponding polyenedials 10 with 2-thio-1,3-dithiole-4,5-dicarbonitrile (9). By the same procedure, the dimethyloctamethine- and the tetramethyl-hexadecamethine-tetrathiafulvalenes 14 and 15, respectively, were obtained. The extended tetrathiafulvalenes represent multistep vinylogous redox systems of the ‘violene type’. They can be oxidized to give the cyanine-like radical cations, e.g. 11sem, 14sem, and 15sem, and the dications, e.g. 11ox, 14ox, and 15ox; their UV/VIS/NIR spectra are reported. The crystal and molecular structure of (all-E)-2,2′-(octa-2,4,6-trien-1,8-diylidene)bis[1,3-dithiole-4,5-dicarbonitrile] (11e) was determined: it is a rod-like, planar molecule; in the crystal, it forms staples along the longest molecule axis. The CV measurements confirm that the redox potentials of 11, 14, and 15 decrease asymptotically with the increasing length of the spacer. Because of the close relationship of the extended tetrathiafulvalenes (ETTF's) to the carotinoids, they are named ‘caroviologenes’; they formally belong to the class of molecular wires.
Additional Material:
11 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19960790522
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