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Oscillator strengths f of the longest wavelength absorption increases with the number n of double bonds and triple bonds in linear polyenes, cyanines, and related π-systems
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45749158041
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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
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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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70349444319
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note
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[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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(a) Das, K. Ph.D. Dissertation, University of Nebraska, Lincoln, 2007; http://digitalcommons.unl.edu/dissertations/AAI3271933.
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70349461816
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note
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(b) Figure S46 and Table S8, Supporting Information.
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66
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70349477292
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Manuscript in preparation.
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Rajca, A.; Miyasaka, M.; Xiao, S.; Boratyński, P.; Pink, M.; Rajca, S. Manuscript in preparation.
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Rajca, A.1
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67
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70349439906
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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.
-
-
-
-
68
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0000503227
-
-
For calculations of overall helix structure for helicenes, see
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For calculations of overall helix structure for helicenes, see: Navaza, I.; Tsoucaris, G.; Le Bas, G.; Navaza, A.; de Rango, C. Bull. Soc. Chim. Belg. 1979, 88, 863-870.
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Navaza, I.1
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70349438095
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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)°.
-
-
-
-
70
-
-
70349471876
-
-
note
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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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-
-
-
71
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33751385495
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Propeller-shape molecule forming crystals with helical morphology
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Propeller-shape molecule forming crystals with helical morphology: Ho, D. M.; Pascal, R. A., Jr. Chem. Mater. 1993, 5, 1358-1361.
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(1993)
Chem. Mater.
, vol.5
, pp. 1358-1361
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Ho, D.M.1
Pascal Jr., R.A.2
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72
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70349105995
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Bending of organic crystals upon irradiation
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Bending of organic crystals upon irradiation: Koshima, H.; Naoko Ojima, N.; Uchimoto, H. J. Am. Chem. Soc. 2009, 131, 6890-6891.
-
(2009)
J. Am. Chem. Soc.
, vol.131
, pp. 6890-6891
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Koshima, H.1
Naoko Ojima, N.2
Uchimoto, H.3
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73
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23944441456
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(a) Reddy, C. M.; Gundakaram, R. C.; Basavoju, S.; Kirchner, M. T.; Padmanabhan, K. A.; Desiraju, G. R. Chem. Commun. 2005, 3945-3947.
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(2005)
Chem. Commun.
, pp. 3945-3947
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-
Reddy, C.M.1
Gundakaram, R.C.2
Basavoju, S.3
Kirchner, M.T.4
Padmanabhan, K.A.5
Desiraju, G.R.6
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74
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33644758155
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(b) Reddy, C. M.; Kirchner, M. T.; Gundakaram, R. C.; Padmanabhan, K. A.; Desiraju, G. R. Chem.; Eur. J. 2006, 12, 2222-2234.
-
(2006)
Chem.; Eur. J.
, vol.12
, pp. 2222-2234
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-
Reddy, C.M.1
Kirchner, M.T.2
Gundakaram, R.C.3
Padmanabhan, K.A.4
Desiraju, G.R.5
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75
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34147099537
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Osuna, R. M.; Ortiz, R. P.; Hernández, V.; Navarrete, J. T.; Miyasaka, M.; Rajca, S.; Rajca, A.; Glaser, R. J. Phys. Chem. C 2007, 111, 4854-4860.
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(2007)
J. Phys. Chem. C
, vol.111
, pp. 4854-4860
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Osuna, R.M.1
Ortiz, R.P.2
Hernández, V.3
Navarrete, J.T.4
Miyasaka, M.5
Rajca, S.6
Rajca, A.7
Glaser, R.8
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78
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0142135375
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-
Absolute configuration for bis(trimethylsilyl)-substituted 8 has been reported
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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.
-
(2003)
J. Phys. Chem. A
, vol.107
, pp. 7692-7696
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Friedman, T.B.1
Cao, X.2
Wang, H.3
Rajca, A.4
Nafie, L.A.5
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79
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0000954764
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Tanaka, K.; Suzuki, H.; Osuga, H. J. Org. Chem. 1997, 62, 4465-4470.
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(1997)
J. Org. Chem.
, vol.62
, pp. 4465-4470
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Tanaka, K.1
Suzuki, H.2
Osuga, H.3
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80
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34748917883
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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
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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: Bossi, A.; Maiorana, S.; Graiff, C.; Tiripicchio, A.; Licandro, E. Eur. J. Org. Chem. 2007, 4499-4509.
-
(2007)
Eur. J. Org. Chem.
, pp. 4499-4509
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Bossi, A.1
Maiorana, S.2
Graiff, C.3
Tiripicchio, A.4
Licandro, E.5
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81
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0042656724
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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
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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: Wachsmann, C.; Weber, E.; Czugler, M.; Seichter, W. Eur. J. Org. Chem. 2003, 2863-2876.
-
(2003)
Eur. J. Org. Chem.
, pp. 2863-2876
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-
Wachsmann, C.1
Weber, E.2
Czugler, M.3
Seichter, W.4
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