Cyclic tetrathiophenes 1, 2, and 3 planarized by dimethylsilyl, sulfur, and sulfone bridges bearing an antiaromatic cycloocatatetraene (COT) core were designed and synthesized to investigate the relationship among the bent angle, paratropicity, and HOMO-LUMO gap of the COT ring. The bent angles of the central COT rings of 1-3 were theoretically estimated and experimentally determined, and it was found that the planarity of the COT ring was finely adjusted in the order of 2 > 3 > 1 by using the small differences in the bond lengths between the bridging units and thiophene rings. From the comparisons of NICS values and calculated HOMO-LUMO gaps of cyclooctatetraene at various bent angles as well as the optimized structures of cyclic tetrathiophenes 1-3, similar enhancement of the paratropicity and narrowing of the HOMO-LUMO gap with decreasing bent angle of the COT rings were shown in both cyclooctatetraene and cyclic tetrathiophenes 1-3. Such predictions were experimentally proved for the first time by means of (1)H NMR and UV-vis measurements of 1-3. In comparison of the (1)H NMR chemical shifts of 1-3 with those of the corresponding precursors, upfield shifts due to a paratropic ring current in the COT ring were observed and the degree of shift increased with increasing planarity of the COT ring. Furthermore the colors of the solutions of 1 (lambda(max) = 483 nm), 2b (lambda(max) = 618 nm), and 3b (lambda(max) = 575 nm) were orange, purple, and red in CH(2)Cl(2), respectively, indicating that the HOMO-LUMO gaps of 1-3 become increasingly narrow with increasing planarity of the COT ring. Reflecting these electronic properties, CV measurements demonstrated the amphoteric redox properties of 1 and 2b, and the radical cation 1(*+), radical anion 1(*-), and dianion 1(2-) were chemically generated and successfully characterized by means of UV-vis, ESR, and NMR spectroscopies.

Cyclooctatetraene (COT), the first 4nπ-electron system to be studied, adopts an inherently nonplanar tub-shaped geometry of D 2d symmetry with alternating single and double bonds, and hence behaves as a nonaromatic polyene rather than an antiaromatic compound. Recently, however, considerable 8π-antiaromatic paratropicity has been shown to be generated in planar COT rings even with the bond alternated D 4h structure. In this review, we highlight recent theoretical and experimental studies on the antiaromaticity of hypothetical and actual planar COT. In addition, theoretically predicted triplet aromaticity and stacked aromaticity of planar COT are also briefly described.

Tetra[2,3-thienylene] planarised by sulphur bridges and radially π-extended with (triisopropylsilyl)ethynyl groups had a narrow HOMO-LUMO gap due to the antiaromatic cyclooctatetraene core, and its single crystal FET device exhibited ambipolar characteristics with hole and electron mobilities of up to 0.40 and 0.18 cm(2) V(-1) s(-1), respectively.

The design and synthesis of a new planar cyclooctatetraene (COT) with protons directly connected to the COT ring was attained by monoannelation with dithieno[3,4-b:3',4'-d]thiophene. The planar structure of the COT core was unambiguously confirmed by X-ray crystallography. The magnetic antiaromaticity of the COT core was found to be higher than that of the previously synthesized planar COTs with olefinic protons, according to the results of (1)H NMR and absorption spectra as well as NICS calculations.

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