スライド 1

Structures and Properties of Bowl-Ｓhaped
Compounds
Tobe Lab.
Kenta Ohtsuka
Contents
1.Singlet Biradical
2. Biradicaloid with 2D and 3D Geometry
3. Bowl-shaped Compounds: Bucky Bowls
-corannulene
-sumanene
4. POAV: A Measure of Bowl Depth
5. Dynamic Process: Bowl-to-Bowl Inversion
6. Theoretical Study for My Target Compound
7. Conclusions and Outlook
Singlet Biradical
p-quinodimethane
o-quinodimethane
Shimizu, A.; Tobe, Y. Angew. Chem.
Int. Ed. 2011, 50, 6906.
Chase, D. T. et al. Angew. Chem. Int. Ed.
2011, 50, 11103 -11106.
S-T gap (kJ/mol) HOMO (eV) LUMO (eV) H-L gap (eV)
Biradical character (%)
1a
78.5
-5.22
-2.61
2.61
30.2
2a
53.9
-5.11
-2.85
2.26
32.5
Aromatic Stabilization Energy (ASE)
biradical character :
y  1-
2T
1 T
2
nHOMO, nLUMO; occupation numbers of HOMO or LUMO
nHOMO - nLUMO 

T 

2


UHF/6-31G*//UB3LYP/6-31G* and Yamaguchi scheme
Yamaguchi, K. Chem. Phys. Lett. 1975, 33, 330.
Properties derived from singlet biradical
S2 g
Two-Photon Absorption
Two-photon absorption is the simultaneous absorption of
two photons of identical or different frequencies in order to
excite a molecule from one state (usually the ground state)
to a higher energy electronic state.
 [a.u.]
Kab = 0.01
0.005
0.001

hn
R
4(1 - y)
U 
1
1 - 2K ab 

U
1 - (1 - y) 2

4
BA
2
hn’
S1u
hn’
S1g
2




2
1
1 - (1 - y) 2
 ; second hyperpolarizability
Kab ; exchange integral
U ; effective coulombic repulsion energy
RBA ; distance between radical-sites
y
rubrene
>1100 GM
67 GM
GM = 10−50 cm4 s photon−1 molecule−1
Motivation
Aaron, G. F. et al. Org. Lett.
2013, 15, 1362-1365.
2D
3D
Motivation
Motivation
Bucky Bowls
the generic name of the bowl-shaped conjugated compounds
corresponding to substructure of fullerenes or the cap structure
of the carbon nanotube.
carbonnanotube
Imamure, K.; Takamiya, K. et al. Chem. Commun., 1999, 1859-1860.
Corannulene
Corannulene is a polycyclic aromatic hydrocarbon with chemical
formula C20H10.
The compound consists of a cyclopentane ring fused by five
benzene rings.
It is of scientific interest because it can be considered as a
fragment of fullerene.
Synthesis of Corannulene
Anna, M. B. et al. Org. Process Res. Dev. 2012, 16, 664-676.
Sumanene
• sumanene is a polycyclic aromatic hydrocarbon and of
scientific interest because the compound can be
considered a fragment of fullerene.
• The core of sumanene is a benzene ring and the
periphery consists of six-membered rings and fivemembered rings.
• Sumanene has three sp3 hybridized carbon atoms at the
benzylic positions.
Synthesis of Sumanene
Sakurai, H.; Daiko, T. et al. J. Am. Chem. Soc. 2005, 127, 11580-11581.
Crystal Packing of Sumanene
3.86 Å
4.5×10-2 cm2V-1s-1
(parallel to π-bowl stacking axis)
0.49×10-2 cm2V-1s-1
(perpendicular to π-bowl stacking axis)
Amaya, T.; Seki, S. et al. J. Am. Chem. Soc.
2009, 131, 408-409.
POAV (P-Orbital Axis Vector)
POAV angle is defined as θσπ-90,
which indicates the extent of the pyramidalization.
For planar compound, POAV angle is 0.
1D Structure
POAV = 0
2D Structure
POAV = 0
Amaya, T.; Sakane, H. et al. Pure Appl. Chem. 2010, 82, 969–978.
Corannulene
Sumanene
Fullerene
Hindy, E. B. et al. J. Am. Chem.
Soc. 2002, 124, 8870-8875.
BD = 0.89 Å
Andrzej, S. et al. J. Am. Chem. Soc.
1996, 118, 339-343.
BD = 1.15 Å
Amaya, T.; Sakane, H. et al. Pure Appl.
Chem. 2010, 82, 969–978.
BD (bowl depth) : Bowl depth is distance between the plane
of the hub benzene ring and the aromatic
carbon rim .
POAV of My Compound
POAV = 5.4
POAV = 7.6
BD(Bowl Depth) of My Compound
0.84 Å
Bowl-to-Bowl Inversion of Corannulene
= 8.63 kcal/mol
• The curvature stems from the presence of a five-membered
ring centered among six-membered rings.
• Corannulene represents bowl-to-bowl inversion and the
energy is 8.63 kcal/mol (B3LYP/6-31G)
(室温で1秒間に200,000回以上回転)
Biedermann, P.U.; Pogodin, S. et al. J. Org. Chem. 1999, 64, 3655-3662.
Bowl-to-Bowl Inversion of Sumanene
= 16.8
kcal/mol
• Bowl-to-bowl inversion energy barrier of
sumanene : 16.8 kcal/mol(B3LYP/6-31G(d))
(室温で1秒間に約1回反転)
Amaya, T.; Sakane, H. et al. Pure Appl. Chem. 2010, 82, 969–978.
Bowl-to-Bowl Inversion of My Compound
= 6.46
kcal/mol
• Bowl-to-bowl inversion energy barrier of
My compound: 6.46 kcal/mol(B3LYP/6-31G(d))
Discussion
coronene
sumanene
my compound
Discussion
Corannulene
My compound
planar structure
planar structure
bowl shaped structure
Bowl shaped structure
Conclusions
・Bucky bowls such as corannulene and sumanene
showed bowl-to-bowl inversion with 8.63 kcal/mol, 16.8
kcal/mol respectively and my compound showed bowlto-bowl inversion with 6.46 kcal/mol.
・POAV, BD, and the barrier for the bowl-to-bowl inversion
of my compound was estimated to be smaller than
those of corannulene and sumanene.This may be
affected by the number of five-membered rings and
bond angle strain.
Outlook
Packing of Corannulene
Application of Two-Photon Absorption
①Two-photon Photodynamic Therapy
By using two-photon absorption, long-wavelength light
that is less susceptible to scattering and not absorbed
by healthy cells can be used for excitation and can be
performed photodynamic therapy to the deep part of
other than the surface .
②Microfabrication
Stereoscopic sulptures can be made at the level of
sub-micrometer by controlling the three-dimensional
location of the polymerization photocurable resin .

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