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Volumn 132, Issue 3, 2010, Pages 1066-1074

Cyclic tetrathiophenes planarized by silicon and sulfur bridges bearing antiaromatic cyclooctatetraene core: Syntheses, structures, and properties

Author keywords

[No Author keywords available]

Indexed keywords

AMPHOTERIC REDOX PROPERTIES; BENT ANGLE; BRIDGING UNITS; C-V MEASUREMENT; CYCLOOCTATETRAENE; DIANIONS; HOMO-LUMO GAPS; NMR CHEMICAL SHIFTS; NMR SPECTROSCOPY; OPTIMIZED STRUCTURES; PLANARITY; RADICAL ANIONS; RADICAL CATIONS; RING CURRENTS; SULFUR BRIDGES; THIOPHENE RING;

EID: 76149084210     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja908161r     Document Type: Article
Times cited : (96)

References (80)
  • 46
    • 10044223309 scopus 로고
    • (b) Askani, R. Chem. Ber. 1969, 102, 3304.
    • (1969) Chem. Ber , vol.102 , pp. 3304
    • Askani, R.1
  • 68
    • 76149106807 scopus 로고    scopus 로고
    • The NICS values (GIAO/HF/6-311+G(d,p)) of the COT ring of monomer and dimer in the X-ray structure of 2a were similar, (16.1 and 16.5) suggesting that there is no aromatic interaction between the COT rings in the packing structure of 2a.
    • The NICS values (GIAO/HF/6-311+G(d,p)) of the COT ring of monomer and dimer in the X-ray structure of 2a were similar, (16.1 and 16.5) suggesting that there is no aromatic interaction between the COT rings in the packing structure of 2a.
  • 73
    • 76149123534 scopus 로고    scopus 로고
    • We thank a reviewer for raising this point
    • We thank a reviewer for raising this point.
  • 74
    • 0000450727 scopus 로고    scopus 로고
    • At the same time, the gap between the HOMO-1 and HOMO considerably increases. See: (a) Nishinaga, T, Komatsu, K, Sugita, N, Lindner, H. J, Richter, J. J. Am. Chem. Soc. 1993, 115, 11642
    • At the same time, the gap between the HOMO-1 and HOMO considerably increases. See: (a) Nishinaga, T.; Komatsu, K.; Sugita, N.; Lindner, H. J.; Richter, J. J. Am. Chem. Soc. 1993, 115, 11642.
  • 76
    • 76149086795 scopus 로고    scopus 로고
    • The observed NMR chemical shifts for the α-protons of 3,3′-bithiophene, 5, 7, 9, and 11 and the carbons of 1 and 12 were assigned according to the calculated NMR chemical shifts (GIAO/HF/6-311+G(2d,p)//B3LYP/6-31G(d,p) level).
    • The observed NMR chemical shifts for the α-protons of 3,3′-bithiophene, 5, 7, 9, and 11 and the carbons of 1 and 12 were assigned according to the calculated NMR chemical shifts (GIAO/HF/6-311+G(2d,p)//B3LYP/6-31G(d,p) level).
  • 77
    • 76149126410 scopus 로고    scopus 로고
    • One reviewer suggested that intramolecular charge trasfer from four thiophenes to COT core may contribute to the longer absorption bands. However, no apparent separation of charge between the thiophene and COT rings was observed in the electrostatic potential surfaces of 1-3 (Figure S30, Furthermore, if the fused thiophene units serve as electron-donating group to the electron-withdrawing COT core, the HOMO level of the COT core is expected to be elevated by the fused thiophene units. However, the HOMO level, 4.95 eV, B3LYP/6-31Gd,p, of hypothetical 11 having planar D2h structure was calculated to be identical to that of D 4h-COT, 4.95 eV, Both results suggest that the contribution of intramolecular charge transfer is less important, Chemical Equation Presented
    • 4h-COT (-4.95 eV). Both results suggest that the contribution of intramolecular charge transfer is less important. (Chemical Equation Presented)


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