Helvetica Chimica Acta
10.1002/hlca.201900049
HELVETICA
[
[
15] L. T. Scott, G. J. DeCicco, J. L. Hyun, G. Reinhardt, ’Decamethyl[5]pericyclyne.
Author Contribution Statement
A novel homoconjugated cyclic polyacetylene’ J. Am. Chem. Soc. 1983, 105,
7
760-7761.
16] L. T. Scott, G. J. DeCicco, J. L. Hyun, G. Reinhardt, ‘Pericyclynes of order [5],
6], [7], and [8]. Simple convergent syntheses and chemical reactions of the
first homoconjugated cyclic polyacetylenes’, J. Am. Chem. Soc. 1985, 107,
546-6555.
M. C. performed the synthesis and characterization work and wrote the
corresponding experimental section. I. C.-Q. conducted the STM
investigations. O. A.-R. and D. B-A. performed the photovoltaic and AFM
experiments. Y. A. performed the early exploratory synthesis work. C. D.
and B. K. solved the crystal structure. J. L. M. and G. R.-O. co-devised and
supervised the STM, AFM and photovoltaic experiments and wrote the
corresponding sections. V. M. and R. C. co-devised the work project and
wrote the original main text.
[
6
[
[
[
17] L. Maurette, C. Tedeschi, E. Sermot, M. Soleilhavoup, F. Hussain, B. Donnadieu,
R. Chauvin, ‘Synthesis and stereochemical resolution of functional
[5]pericyclynes’, Tetrahedron 2004, 60, 10077-10098.
18] L. Leroyer, C. Zou, V. Maraval, R. Chauvin, ‘Synthesis and stereochemical
resolution of
a [6]pericyclynedione: versatile access to pericyclynediol
precursors of carbo-benzenes’, C. R. Chimie 2009, 12, 412-429.
19] A. Rives, I. Baglai, C. Barthes, V. Maraval, N. Saffon-Merceron, A. Saquet, Z.
Voitenko, Y. Volovenko, R. Chauvin, ‘Carbo-cyclohexadienes vs. carbo-
benzenes: structure and conjugative properties’, Chem. Sci. 2015, 6, 1139-1149.
References
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2
[20] C. Barthes, A. Rives, V. Maraval, E. Chelain, T. Brigaud, R. Chauvin, ‘First
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C. Ni, J. Hu, 'The unique fluorine effects in organic reactions: recent facts and
insights into fluoroalkylation ', Chem. Soc. Rev. 2016, 45, 5441-5454.
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two-photon absorption', French-Ukr. J. Chem. 2018, 6, 9-17.
[22] In D2h symmetry, the dipole moment µ is zero and the number of independent
components of the traceless quadrupolar tensor Qij is two: A. D. Buckingham,
A. D. in Physical Chemistry, an Advanced Treatise, H. Eyring, W. Jost, D.
Henderson Eds., Vol. 4, Chapt. 8, Table I, p. 361, Academic: New York, 1970. In
the present hexaaryl quadrupolar series, the increase in polarity is revealed by
the differences in the in-plane amplitude (|Qxx + Q |= |Q |) and in-plane
[
[
4]
5]
For the original reference on carbo-mers, see: R. Chauvin, ‘”Carbomers”. I. A
general concept of expanded molecules’, Tetrahedron Lett. 1995, 36, 397-400.
For original references on carbo-benzenes, see: Y. Kuwatani, N. Watanabe, I.
Ueda,
,2,4,5,7,8,10,11,13,14,16,17-Dodecadehydro[18]annulenes
Symmetry', Tetrahedron Lett. 1995, 46, 119-122.
'Synthesis
of
the
First
3,6,9,12,15,18-Hexa-substituted-
1
with D -
6h
yy
zz
anisotropy (Δxy = |Qxx – Q |) between 1a (|Q | = 77.7 D. Å, Δ = 9.1 D. Å) and 2a
yy
zz
xy
[
[
[
[
6]
7]
8]
9]
R. Chauvin, ‘”Carbomers”. II. En route to [C,C]
6
Carbo-Benzene’, Tetrahedron
(|Qzz| = 35.6 D. Å, Δxy = 174.6 D. Å). For comparison, in the di(tertiobuty)diaryl
dipolar series similar values (with respect to the molecule centroid) are
calculated for 1b (µ = 0.94 D, |Q | = 61.6 D. Å, Δ = 3.1 D. Å) and 2b (µ = 0.78 D,
Lett. 1995, 36, 401-404.
R. Suzuki, H. Tsukuda, N. Watanabe, Y. Kuwatani, I. Ueda, Tetrahedron 1998,
4, 2477-2496.
zz
xy
5
zz
|Q | = 18.5 D. Å, Δxy = 164.4 D. Å), respectively. Therefore, bis-
K. Cocq, C. Lepetit, V. Maraval, R. Chauvin, ‘”Carbo-aromaticity” and novel
carbo-aromatic compounds’, Chem. Soc. Rev. 2015, 44, 6535-6559.
trifluoromethylation of 1a or 1b results in a 2 or 3 times lower value of |Q | and
zz
in a 20 or 50 times higher value of Δxy , in 2a or 2b, respectively.
K. Cocq, C. Barthes, A. Rives, V. Maraval, R. Chauvin, 'Synthesis of functional
carbo-benzenes with functional properties: the C2 tether key', Synlett 2019, 30,
[23] P. J. Bruna, F. Grein, 'Quadrupole, octopole, and hexadecapole electric
moments of ∑, ∏, ∆ and F electronic states: Cylindrically asymmetric charge
density distributions in linear molecules with nonzero electronic angular
momentum', J. Chem. Phys. 2007, 127, 074107-1-12
3
0-43.
[
[
10] K. Cocq, N. Saffon-Merceron, A. Poater, V. Maraval, R. Chauvin, ‘Aromatic
rings and aromatic rods: nonplanar character of an indeno-
dehydro[14]annulene’, Synlett 2016, 27, 2105-2112.
[24] Calculations at the B3PW91/6-31G(d,p) level with the program Firefly 8.1.1: A.
A.
Granovsky,
Firefly
version
8
11]
C. Zhu, C. Duhayon, D. Romero-Borja, J.-L. Maldonado, G. Ramos-Ortíz, A.
Saquet, V. Maraval, R. Chauvin, ‘Hexaaryl-carbo-benzenes revisited: a novel
synthetic route, crystallographic data, and prospects of electrochemical
behavior’, New J. Chem. 2017, 41, 3908-3914.
the GAMESS (US) source code; M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S.
T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen,
S. Su, T. L. Windus, M. Dupuis, J. A. Montgomery, 'General atomic and
molecular electronic structure system', J. Comput. Chem. 1993, 14, 1347-1363.
[25] CCDC 1895113 contains the supplementary crystallographic data for 2b. These
data can be obtained free of charge from The Cambridge Crystallographic Data
[
12] D. Listunov, C. Duhayon, A. Poater, S. Mazères, A. Saquet, V. Maraval, R.
Chauvin, ‘Steric/p-electronic insulation of the carbo-benzene ring: dramatic
effects of tert-butyl versus phenyl crowns on geometric, chromophoric, redox,
and magnetic properties’, Chem. Eur. J. 2018, 24, 10699-10710.
-
1
[
[
13]
C. Zhu, C. Duhayon, A. Saquet, V. Maraval, R. Chauvin, ‘Selective access to p-
dialkyl-carbo-benzenes from a [6]pericyclynedione : the n-butyl nucleophile
model for a metal switch study’, Can. J. Chem. 2017, 95(4), 454-459.
[26] Crystal data for 2b. C52 H36 F , M = 774.85 g mol , Monoclinic, a = 6.26760(10),
6
3
b = 16.5031(3), c = 19.6608(3) Å, α = g =90°, b = 92.530(1)°, V = 2031.63(6) Å , T
-
1
= 100 K, space group P2 , Z = 2, µ(Cu-Ka) = 0.757 mm , 16000 reflections
1
14] C. Zhu, A. Rives, C. Duhayon, V. Maraval, R. Chauvin, ‘Lipidic carbo-benzenes:
molecular probes of magnetic anisotropy and stacking properties of a-
graphyne’, J. Org. Chem. 2017, 82, 925-935.
measured, 6630 unique (Rint = 0.028), 5656 reflections used in the calculations
[
I > 3s(I)], 548 parameters, R1 = 0.0368, wR2 = 0.0459.
[27] O. Roshal, C. Zhu, V. Maraval, R. Chauvin, 'Spectral properties of dioctyl-carbo-
benzene', manuscript in preparation. See also the Supporting Information of
ref. [12].
7
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