Synthesis and Crystallochromy of 1,4,7,10-Tetraalkyltetracenes
FULL PAPER
136.58 ppm; elemental analysis calcd (%) for C30H36: C 90.85, H 9.15;
found C 90.93, H 9.32.
Crystal data for 1d-form B: Crystal dimensions: 0.50ꢃ0.12ꢃ0.05 mm,
C34H44, M=452.72, T=223 K, triclinic, space group P1, a=5.392(6), b=
¯
8.66(1), c=15.19(2) ꢁ, a=101.41(3), b=90.45(4), g=99.35(6)8, V=
1,4,7,10-Tetrabutyltetracene (1d): Mixture of yellow and red solids (m.p.
128–1318C); 1H NMR (500 MHz, CDCl3): d=1.03 (t, J=7.3 Hz, 12H),
1.53–1.57 (m, 8H), 1.84–1.90 (m, 8H), 3.19 (t, J=7.8 Hz, 8H), 7.14 (s,
4H), 8.81 ppm (s, 4H); 13C NMR (126 MHz, CDCl3): d=14.16, 23.03,
32.31, 32.95, 123.22, 123.87, 128.99, 131.00, 136.67 ppm; elemental analy-
sis calcd (%) for C34H44: C 90.20, H 9.80; found C 90.27, H 9.71. The red
solid (form A: m.p. 128–1308C) was produced by high-rate evaporation
using a rotary evaporator from a CHCl3 solution, and the yellow solid
(form B: m.p. 114–1168C) was obtained by rate-independent evaporation
using a rotary evaporator from a hexane solution and then manual re-
moval of a small amount of red solid.
673(1) ꢁ3, Z=1, 1calcd =1.116 gcmꢁ3
, , 5358 reflections
m=0.062 mmꢁ1
measured, 2959 unique, 242 parameters refined, D1max =0.38 eꢁꢁ3, R1 =
0.084 (2045 with [I>2s(I)]), wR=0.209 (all data).
Crystal data for 1e: Crystal dimensions: 0.12ꢃ0.10ꢃ0.05 mm, C38H52,
¯
M=508.83, T=223 K, triclinic, space group P1, a=5.146(4), b=11.28(1),
c=13.55(1) ꢁ, a=85.63(2), b=84.72(3), g=81.70(3)8, V=773(1) ꢁ3, Z=
1, 1calcd =1.092 gcmꢁ3
,
m=0.061 mmꢁ1
,
6174 reflections measured,
3466 unique, 276 parameters refined, D1max =0.25 eꢁꢁ3, R1 =0.065 (2048
with [I>2s(I)]), wR=0.164 (all data).
Crystal data for 1 f: Crystal dimensions: 0.33ꢃ0.05ꢃ0.01 mm, C42H60,
M=564.90, T=173 K, monoclinic, space group C2/c, a=33.04(3), b=
1,4,7,10-Tetrapentyltetracene (1e): Orange solid (m.p. 129–1308C);
1H NMR (500 MHz, CDCl3): d=0.95 (t, J=7.2 Hz, 12H), 1.41–1.55 (m,
16H), 1.86–1.92 (m, 8H), 3.20 (t, J=7.7 Hz, 8H), 7.14 (s, 4H), 8.81 ppm
(s, 4H); 13C NMR (126 MHz, CDCl3): d=14.15, 22.68, 29.85, 32.17, 33.20,
123.22, 123.87, 129.00, 130.99, 136.72 ppm; elemental analysis calcd (%)
for C38H52: C 89.72, H 10.30; found C 89.95, H 10.39.
1,4,7,10-Tetrahexyltetracene (1 f): Red solid (m.p. 108–1098C); 1H NMR
(500 MHz, CDCl3): d=0.93 (t, J=7.0 Hz, 12H), 1.36–1.44 (m, 16H),
1.51–1.56 (m, 8H), 1.86–1.92 (m, 8H), 3.22 (t, J=7.7 Hz, 8H), 7.17 (s,
4H), 8.84 ppm (s, 4H); 13C NMR (126 MHz, CDCl3): d=14.17, 22.72,
29.65, 30.14, 31.84, 33.27, 123.26, 123.91, 129.02, 131.01, 136.78 ppm; ele-
mental analysis calcd (%) for C42H60: C 89.29, H 10.71; found C 89.44, H
10.60.
4.735(3), c=26.41(2) ꢁ, b=123.586(8)8, V=3442(5) ꢁ3, Z=4, 1calcd
=
1.090 gcmꢁ3 m=0.060 mmꢁ1
, , 13423 reflections measured, 3891 unique,
190 parameters refined, D1max =0.22 eꢁꢁ3
2s(I)]), wR=0.232 (all data).
, R1 =0.136 (2245 with [I>
Calculations: The lowest-energy absorption band of the tetracene mole-
cule, on the basis of geometry obtained by X-ray analysis, was calculated
using the TD-DFT B3LYP/6-31G* method with Gaussian03.[16] The exci-
ton displacement energy (DEexciton), corresponding to the spectral shift
between a pair of molecules, is given by the following dipole-dipole equa-
2
tion: DEexciton =jmj (1ꢁ3cos2q)/r3, where m is the transition dipole and q
and r are the angle and distance between two transition dipoles, respec-
2
tively.[17] The term jmj directly depends on the absorption coefficient of
the molecule. The term (1ꢁ3cos2q)/r3 determines the geometrical rela-
tionship of transition dipoles correlated with the crystal structure. Wheth-
er a shift is blue or red depends on the critical angle q=54.78, above
which the shift is blue and below which the shift is red. m was calculated
by the TD-DFT calculations, and the q and r were obtained from the ge-
ometry of the crystal structures. Calculations of DEexciton were performed
on the nearest-neighbor molecules within 20 ꢁ. The total energy dis-
X-ray crystallography: Single crystals suitable for X-ray analysis were ob-
tained by slow evaporation from the following solvents: Et2O-toluene for
1a, toluene for 1b and 1d–f, benzene for 1c. X-ray diffraction data were
collected on a Rigaku/Mercury CCD area-detector diffractometer with
graphite-monochromated MoKa (a=0.71070 ꢁ) radiation, f and w scans
to a maximum 2q value of 55.08. The structures were solved by a direct
method using SIR92.[22] All non-hydrogen atoms were refined anisotropi-
cally by full-matrix least-squares on F2 using SHELXL97.[23] Hydrogen
atoms of 1a-e were refined isotropically, and those of 1 f were positioned
geometrically and refined using a riding model. All calculations were per-
formed using the teXsan program package.[24] CCDC-723050 (1a),
CCDC-723051 (1b), CCDC-723052 (1c), CCDC-642337 (1d-form A),
CCDC-642338 (1d-form B), CCDC-723053 (1e), and CCDC-723054 (1 f)
contain supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallographic
placement was then summed up to be Eshift
.
Acknowledgements
The authors are grateful to Prof. Dr. Shinya Matsumomo (Yokohama
National University) for discussions about intermolecular interactions.
We also thank the Instrument Center of the Institute for Molecular Sci-
ence for X-ray structural analyses. This work was supported by a Grant-
in-Aid (No. 20550128) from the Ministry of Education, Culture, Sports,
Science and Technology, Japan.
Crystal data for 1a: Crystal dimensions: 0.50ꢃ0.10ꢃ0.05 mm, C22H20,
¯
M=284.40, T=223 K, triclinic, space group P1, a=5.0089(5), b=
13.386(1), c=17.349(2) ꢁ, a=83.817(8), b=89.80(1), g=88.04(1)8, V=
1155.8(2) ꢁ3, Z=3, 1calcd =1.226 gcmꢁ3, m=0.069 mmꢁ1, 9301 reflections
measured, 5192 unique, 418 parameters refined, D1max =0.29 eꢁꢁ3, R1 =
0.061 (4139 with [I>2s(I)]), wR=0.133 (all data).
Crystal data for 1b: Crystal dimensions: 0.40ꢃ0.04ꢃ0.01 mm, C26H28,
¯
[2] a) A. S. Paraskar, A. R. Reddy, A. Patra, Y. H. Wijsboom, O.
2006, 8, 273; c) R. Schmidt, S. Gçttling, D. Leusser, D. Stalke, A.-M.
gen, H. Hopf, A. Del Guerzo, J.-P. Desvergne, H. Bouas-Laurent,
T. W. Kelley, D. V. Muyres, S. E. Fritz, M. F. Toney, C. D. Frisbie, J.
Am. Chem. Soc. 2005, 127, 3997; f) S. A. Odom, S. R. Parkin, J. E.
[3] a) I. Kaur, W. Jia, R. P. Kopreski, S. Selvarasah, M. R. Dkmeci, C.
Giershner, C. A. Landis, S. R. Parkin, J. B. Sherman, R. C. BakusII,
M. L. Lefenfeld, T. Siegrist, M. L. Steigerwald, C. Nuckolls, J. Am.
M=340.51, T=173 K, triclinic, space group P1, a=3.9992(4), b=
9.4908(1), c=12.9789(9) ꢁ, a=69.22(2), b=87.00(2), g=78.94(2)8, V=
451.94(6) ꢁ3, Z=1, 1calcd =1.251 gcmꢁ3, m=0.070 mmꢁ1, 3665 reflections
measured, 2014 unique, 174 parameters refined, D1max =0.39 eꢁꢁ3, R1 =
0.056 (1658 with [I>2s(I)]), wR=0.138 (all data).
Crystal data for 1c: Crystal dimensions: 0.40ꢃ0.04ꢃ0.01 mm, C30H36,
¯
M=396.61, T=223 K, triclinic, space group P1, a=5.058(4), b=9.292(8),
c=12.800(10) ꢁ, a=103.76(2), b=90.45(4), g=104.02(2)8, V=
565.6(7) ꢁ3, Z=1, 1calcd =1.164 gcmꢁ3, m=0.065 mmꢁ1, 4576 reflections
measured, 2014 unique, 208 parameters refined, D1max =0.22 eꢁꢁ3, R1 =
0.076 (1775 with [I>2s(I)]), wR=0.160 (all data).
Crystal data for 1d-form A: Crystal dimensions: 0.50ꢃ0.03ꢃ0.03 mm,
C34H44, M=452.72, T=223 K, monoclinic, space group C2/c, a=33.27(4),
b=4.739(4), c=21.54(2) ꢁ, b=90.45(4), g=127.46(1)8, V=2695(5) ꢁ3,
Z=4, 1calcd =1.116 gcmꢁ3 m=0.062 mmꢁ1
, , 10890 reflections measured,
3056 unique, 242 parameters refined, D1max =0.35 eꢁꢁ3, R1 =0.086 (1613
with [I>2s(I)]), wR=0.185 (all data).
Chem. Eur. J. 2010, 16, 890 – 898
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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