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Volumn 74, Issue 19, 2009, Pages 7504-7513

Functionalized thiophene-based [7]helicene: Chirooptical properties versus electron delocalization

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL GROUPS; BENZODITHIOPHENE; BUILDING BLOCKES; CHEMICAL EQUATIONS; CHIROOPTICAL PROPERTIES; ELECTRON DELOCALIZATION; FUNCTIONALIZED; HELICENES; SINGLE CRYSTAL X-RAY ANALYSIS; TERMINAL POSITION;

EID: 70349466668     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo901769c     Document Type: Article
Times cited : (54)

References (82)
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    • Racemic [5], [7], [9], [11], [13]helicenes with alternate thiophene and benzene rings: (a)
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    • The band gaps based upon extrapolation of the calculated B3LYP-6- 31G(d) HOMO-LUMO gaps are 4.1, 2.5, and 2.9 eV for cross-conjugated carbon-sulfur [n]helicenes, conjugated [n]helicenes with alternating thiophene and benzene rings, and conjugated all-benzene [n]helicenes, respectively: Tian, Y.-H.; Park, G.; Kertesz, M. Chem. Mater. 2008, 20, 3266-3277.
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    • note
    • [n]Helicenes composed of benzene rings, possessing conjugated systems, have an estimated band gap of 2.5 eV, based upon extrapolation of experimental UV - vis absorption spectra (ref 15b).
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    • note
    • (b) Figure S46 and Table S8, Supporting Information.
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    • note
    • In the X-ray structure of [7]helicene rac-1, relatively high residual electron densities near bromine and sulfur atoms remained unassigned. We postulate that these are artifacts from multiply twinned crystal, that is, in addition to the major domain that was used to integrate the data, multiple minor domains were indexed; however, they could not satisfactorily be included in the data reduction. Consequently, variations for chemically equivalent bond lengths and angles and higher than usual standard uncertainties are found. Nevertheless, the X-ray data provide unequivocal confirmation of the structure for rac-1 and a reasonably accurate helix shape.
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    • note
    • For 2, mean deviation from a calculated least-squares plane including two bromines, benzene ring, and two thiophene rings (Br1, Br2, S1, S2, C1-C10) is 0.0781 Å. The C1-C3-C7-C9 torsion angle (along the inner helix) is 12.8(7)°.
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    • note
    • Distance between the least-squares planes, including benzene ring and two thiophene rings (S1, S2, C1-C10), for the adjacent molecules of 2 slip-stacked (π-stacked) along the b-axis.
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    • Absolute configuration for bis(trimethylsilyl)-substituted 8 has been reported
    • Absolute configuration for bis(trimethylsilyl)-substituted 8 has been reported: Friedman, T. B.; Cao, X.; Wang, H.; Rajca, A.; Nafie, L. A. J. Phys. Chem. A 2003, 107, 7692-7696.
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    • For TMS-substituted [7]helicene 13, a rather low value of [α]D=870 (chloroform), corresponding to [Φ] = 4760, was reported, but the chirooptical data and determination of optical purity are deficient
    • For TMS-substituted [7]helicene 13, a rather low value of [α]D=870 (chloroform), corresponding to [Φ] = 4760, was reported, but the chirooptical data and determination of optical purity are deficient: Bossi, A.; Maiorana, S.; Graiff, C.; Tiripicchio, A.; Licandro, E. Eur. J. Org. Chem. 2007, 4499-4509.
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    • For the most studied all-phenylene [6]helicenes, the relationship between the crystal structure (substituent-induced changes in helical shape) and optical rotation could not be established
    • For the most studied all-phenylene [6]helicenes, the relationship between the crystal structure (substituent-induced changes in helical shape) and optical rotation could not be established: Wachsmann, C.; Weber, E.; Czugler, M.; Seichter, W. Eur. J. Org. Chem. 2003, 2863-2876.
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    • Wachsmann, C.1    Weber, E.2    Czugler, M.3    Seichter, W.4


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.