Mori et al.
(M+, 33%), 612 (19), 306 (16), 207 (23), 152 (10), 151 (100), and
121 (10). HRMS (EI): 780.5337. C51H72O6 requires 780.5329.
EA: Found: C, 78.23; H, 9.30%. Calcd for C51H72O6: C, 78.42;
O, 12.29; H, 9.29. Specific rotation: [R]25D -25.2 ( 5.8° (c 0.10,
CHCl3).
calculations) and was thus used to obtain the final Boltzmann
distribution at 298 K of the conformers. Details are reported in
Supporting Information.
All excited-state calculations have been performed at the
optimized ground-state geometries and thus correspond to vertical
transitions. The CD (and UV-vis) spectra of 1 and 2 were simulated
on the basis of time-dependent density functional theory (TD-
DFT)29 with the BH-LYP49 functional and employing the TZVP
basis set. The program module escf50 has been used in these TD-
DFT treatments. The CD spectra were simulated by overlapping
Gaussian functions for each transition where the width of the band
at 1/e height is fixed at 0.4 eV and the resulting intensities of the
combined spectra were scaled to the experimental values. As usual,
the calculated band intensities are larger than their experimental
counterparts and are thus scaled to facilitate comparison with
experiment. The somewhat smaller scaling factors found (1/5 and
1/20, for 1 and 2, respectively, in contrast to standard 1/2-1/3)
are probably due to our ignorance of the dynamic behavior in the
present theoretical treatments (see also ref 26 for more discussion).
Because of a systematic overestimation of the transition energies
compared to the experiment in the BH-LYP calculations, the spectra
were uniformly shifted by 0.5 eV. The optical rotations at the
sodium-D line wavelength of 1 and 2 were also calculated at the
TD-DFT-BH-LYP method using Dunning’s aug-cc-pVDZ51 and the
aug-SVP52 basis-sets (H, [3s2p], C/O, [4s3p2d]). The rotational
strengths from the length-gauge representation, which are known
to be numerically more robust, were used throughout. It is known
that in the absence of GIAOs, these values are origin-dependent.
Strictly speaking, the calculated optical rotations and CD intensities
can only be compared to experimental values when they are origin-
independent, but the length and velocity rotational strengths
converge to the same value in the complete basis-set limit. With
our relatively large triple-ú type AO basis-sets, the differences
between both representations were negligible (differences are mostly
less than 2-3%).
Octakis(2-methoxy-4-methyl-5-(R)-2-methylpropyloxytolyl)-
biphenylene (4). Yield: 3%. 1H NMR: 0.90 (24H, t, J ) 7.6 Hz),
1.17 (6H, d, J ) 6.0 Hz), 1.49 (8H, pseudo sept, J ) 7.6 Hz), 1.63
(8H, pseudo sept, J ) 7.8 Hz), 2.04 (24H, s), 2.19 (16H, s), 3.74
(24H, s), 3.96 (8H, sxt, J ) 6.0 Hz), 6.40 (8H, s), and 6.62 (8H,
s). 13C NMR: 9.8, 16.4, 16.5, 19.5, 29.2, 55.9, 76.2, 113.0, 115.7,
124.8, 125.9, 126.62, 137.8, 147.9, 145.0, and 151.2. MS (FD):
m/z ) 1802.16 (M+ + 1). MS (FAB): m/z ) 1802.17 (M+ + 1).
C116H152O16 requires 1801.11. Specific rotation: [R]25 -15.6 (
D
4.1° (c 0.10, CHCl3).
1,3,5,7,9-Pentakis[p-(R)-methylpropyloxyphenyl]coran-
1
nulene (5). Yield: 45%. H NMR: 1.03 (15H, t, J ) 7.5 Hz),
1.36 (15H, d, J ) 6.0 Hz), 1.68 (5H, pseudo sept, J ) 7.5 Hz),
1.82 (5H, pseudo sept, J ) 7.5 Hz), 4.38 (5H, pseudo sxt, J )
6.0 Hz), 6.97 (10H, d, J ) 8.6 Hz), 7.54 (10H, d, J ) 8.6 Hz), and
7.76 (5H, s). 13C NMR: 10.0, 19.5, 29.4, 75.2, 116.0, 125.3, 129.4,
131.3, 132.2, 135.3, 141.8, and 158.2. HRMS (FAB): 990.5231.
C70H70O5 requires 990.5223. EA: Found: C, 84.58; H, 7.08%.
Calcd for C70H70O5: C, 84.81; H, 7.12; O, 8.07. Specific rotation:
[R]25 -45.8 ( 4.5° (c 0.10, CHCl3).
D
Technical Details of the Quantum Chemical Computations.
All calculations were performed on Linux-PCs using the TURBO-
MOLE 5.8 program suite.43 All conformers were fully optimized
at the dispersion-corrected DFT-D-B-LYP level44 employing C2,
C3, or C5 symmetry constraint, where appropriate, by using an AO
basis set of valence triple-ú quality with a set of polarization
functions (denoted as TZVP;45 in standard notation: H, [3s1p], C/O,
[5s3p1d]), and numerical quadrature grid m4. The most stable Tg-
conformation was employed for the chiral alkyl group throughout
this study.26 This conformation was found also in the X-ray crystal
structures of 2 and 3 in this study (Vide infra). The resolution of
identity (RI) approximation47 was employed in all DFT-D-B-LYP
calculations, and the corresponding auxiliary basis sets were taken
from the TURBOMOLE basis-set library. Subsequent single-point
energy calculations were performed with the spin-component-scaled
(SCS)-MP2 method22 with a TZVPP basis-set that has additional
d/f and p/d functions on non-hydrogen and hydrogen atoms,
respectively. It has been shown that this simple modification of
the standard MP2 scheme, termed SCS-MP2, leads to dramatic
improvements in accuracy of calculated energies, particularly for
molecules with weak interactions where standard DFT fails.48 The
method is expected to provide the most accurate relative energies
(comparable to the computationally highly demanding CCSD(T)
Acknowledgment. T.M. thanks the Alexander von Hum-
boldt-Stiftung for the fellowship. We thank Drs. Christian Mu¨ck-
Lichtenfeld, Christian Diedrich, and Manuel Piacenza for
technical assistance and fruitful discussion of the theoretical data.
Financial support of this work by a Grant-in-Aid for Scientific
Research from the Ministry of Education, Culture, Sports,
Science, and Technology of Japan to T.M. is gratefully
acknowledged.
Supporting Information Available: Details of experimental
procedure and computation, X-ray crystallographic structure de-
termination (CCDC 650013 and 650014) as well as CIF files of 2
and 3, cyclic voltammometric studies of 2 and 3, 1H and 13C NMR
charts and theoretical and experimental UV-vis and CD spectra
of 1-5 under a variety of conditions, and Cartesian coordinates of
the optimized geometries of a variety of conformations of 1-5.
This material is available free of charge via the Internet at
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