Y. Imai, Y. Matsubara et al.
FULL PAPER
to stand at room temperature. After 2–7 d, colored crystals [I from
rac-1/2,5Me-BQ system (7 mg) and II from rac-1/2Cl-5Me-BQ sys-
tem (9 mg)] were found to be deposited and were subsequently col-
lected. The weight of each type of crystal is the total crop of the
crystals obtained in a single batch.
Kα) = 0.290 mm–1, 7881 reflections measured, 2969 unique, final
R(F2) = 0.0352 using 2686 reflections with I Ͼ 2.0σ(I), R(all data)
= 0.0394, T = 115(2) K.
Theoretical Calculations of Electron Affinities of BQ Derivatives:
The electron affinities of the three BQ derivatives were calculated
by the hybrid density functional theory (B3LYP)[13] with the cc-
pVDZ basis set.[14] The calculations were carried out using the
GAUSSIAN 03 program.[15]
Formation of a CT Complex Including Toluene: rac-1 (0.04 mmol)
and 2,5-substituted BQ (0.12 mmol) were dissolved in toluene (4–
5 mL) with heating. Each solution was allowed to stand at room
temperature. After 5–7 d, the respective colored crystals [III from
rac-1/2,5Me-BQ system (7 mg), IV from rac-1/2Cl-5Me-BQ system
(9 mg), and V from rac-1/2,5Cl-BQ system (8 mg)] were deposited
and collected. The weight of each type of crystal is the total crop
of the crystals obtained in a single batch.
Supporting Information (see also the footnote on the first page of
this article): UV/Vis spectra of rac-1, 2,5Cl-BQ, and a mixture of
rac-1 and 2,5Cl-BQ in benzene or toluene solution.
Acknowledgments
Measurement of DRS of CT Complex: The DRS of the crystals
were measured using a Hitachi U-4000 spectrometer.
This study was supported by the Ministry of Education, Culture,
Sports, Science and Technology, Japan (a Grant-in-Aid for Scien-
tific Research, No. 20750115) and the Kansai Research Foundation
for Technology Promotion.
Measurement of UV/Vis Spectra: The UV/Vis spectra were mea-
sured using a Shimadzu UV-2400PC spectrometer.
X-ray Crystallographic Studies
The X-ray diffraction data for single crystals were collected using
a Bruker Apex instrument. The crystal structures were solved by
the direct method[9] and refined by full-matrix least-squares using
SHELX97.[10] The diagrams were drawn using PLATON.[11] The
absorption corrections were performed using SADABS.[12] The
non-hydrogen atoms were refined with anisotropic displacement
parameters, and the hydrogen atoms were included in the models
at their calculated positions in the riding-model approximation.
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Atwood, J. E. D. Davies, D. D. MacNicol, F. Vögtle (Eds.),
Comprehensive Supramolecular Chemistry, Pergamon Press, Ox-
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clopedia of Supramolecular Chemistry, Marcel Dekker, New
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47, 7885–7888; d) K. Kodama, Y. Kobayashi, K. Saigo, Chem.
Eur. J. 2007, 13, 2144–2152; e) K. Kodama, Y. Kobayashi, K.
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ata, K. Kawaguchi, T. Sato, R. Kuroda, Y. Matsubara, Org.
Lett. 2007, 9, 3457–3460 and references cited therein.
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N. Tajima, T. Sato, R. Kuroda, Y. Matsubara, Tetrahedron
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Tajima, R. Kuroda, Y. Matsubara, Eur. J. Org. Chem. 2008,
4784–4789.
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Y. Imai, N. Tajima, T. Sato, R. Kuroda, Chirality 2002, 14,
604–609; c) F. Toda, M. Senzaki, R. Kuroda, Chem. Commun.
2002, 1788–1789; d) R. Kuroda, Y. Imai, N. Tajima, Chem.
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CCDC-706420 (for I), -679179 (for II), -706242 (for III), -696153
(for IV), and -706241 (for V) contain the crystallographic data for
this article. These data can be obtained free of charge via
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge
Crystallographic Data Centre, 12, Union Road, Cambridge
CB21EZ, UK; Fax: +44-1223-336-033; deposit@ccdc.cam.ac.uk].
I: 0.5C20H14O2·0.5C8H8O2·0.5C6H6, M = 250.28, monoclinic,
space group C2/c,
a = 14.5266(12), b = 12.7974(10), c =
13.9484(11) Å, β = 95.2280(10)°, V = 2582.3(4) Å3, Z = 8, Dc =
1.288 gcm–3, µ(Mo-Kα) = 0.083 mm–1, 7905 reflections measured,
2972 unique, final R(F2) = 0.0430 using 2593 reflections with I Ͼ
2.0σ(I), R(all data) = 0.0492, T = 115(2) K.
II: 0.5C20H14O2·0.5C7H5O2Cl1·0.5C6H6, M = 260.49, monoclinic,
space group C2/c,
a
=
14.5320(10),
b
=
12.7450(10),
c
=
=
13.9860(10) Å, β = 95.267(2)°, V = 2579.4(3) Å3, Z = 8, Dc
1.342 gcm–3, µ(Mo-Kα) = 0.187 mm–1, 7872 reflections measured,
2977 unique, final R(F2) = 0.0491 using 2557 reflections with I Ͼ
2.0σ(I), R(all data) = 0.0565, T = 130(2) K.
III: C20H14O2·C8H8O2·C7H8 M = 514.59, monoclinic, space group
Cc, a = 14.4969(8), b = 12.9791(7), c = 14.0426(7) Å, β =
94.2330(10)°, V = 2635.0(2) Å3, Z = 4, Dc = 1.297 gcm–3, µ(Mo-
Kα) = 0.084 mm–1, 11360 reflections measured, 3054 unique, final
R(F2) = 0.0440 using 2701 reflections with I Ͼ 2.0σ(I), R(all data)
= 0.0497, T = 115(2) K.
[5] Y. Imai, K. Kamon, T. Kinuta, N. Tajima, T. Sato, R. Kuroda,
Y. Matsubara, Cryst. Growth Des. 2008, 8, 3493–3496.
[6] As determined by a PLATON geometry calculation.
[7] The distance between the center of 2,5-substituted BQ and the
average plane of the naphthol 10-membered ring.
[8] The electron affinities of these three molecules were calculated
by the hybrid density functional theory (B3LYP) with the cc-
pVDZ basis set. The calculations were carried out using the
GAUSSIAN 03 program.
IV: C20H14O2·C7H5O2Cl1·C7H8, M = 535.01, monoclinic, space
group Cc, a = 14.4557(9), b = 12.8781(8), c = 14.0147(9) Å, β =
94.1710(10)°, V = 2602.1(3) Å3, Z = 4, Dc = 1.366 gcm–3, µ(Mo-
Kα) = 0.187 mm–1, 11259 reflections measured, 3036 unique, final
R(F2) = 0.0420 using 2762 reflections with I Ͼ 2.0σ(I), R(all data)
= 0.0456, T = 115(2) K.
V: C20H14O2·C6H2O2Cl2·C7H8, M = 555.42, monoclinic, space
group Cc, a = 14.4522(9), b = 12.8116(8), c = 14.0348(9) Å, β =
94.1430(10)°, V = 2591.8(3) Å3, Z = 4, Dc = 1.423 gcm–3, µ(Mo-
[9] G. M. Sheldrick, SHELX97: Program for the Solution of Crys-
tal Structures, University of Göttingen, Germany, 1997.
2524
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Eur. J. Org. Chem. 2009, 2519–2525