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Ohmae T, Nishinaga T, Wu M, Iyoda M: Cyclic tetrathiophenes planarized by silicon and sulfur bridges bearing antiaromatic cyclooctatetraene core: syntheses, structures, and properties. J Am Chem Soc. 2010 Jan 27;132(3):1066-74.
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. |
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