Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta...
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Transcript of Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta...
Synthesis and Properties of Tetracyclopenta def, jkl, pqr,
vwxtetraphenylene
Tobe Lab.Kenta Ohtsuka
Contents
1. Introduction -Singlet biradical
2. Results and discussion
3. Conclusion
4. Next plan
Singlet Biradical
UHF/6-31G*//UB3LYP/6-31G* and Yamaguchi schemeYamaguchi, K. Chem. Phys. Lett. 1975, 33, 330.
nHOMO, nLUMO; occupation numbers of HOMO or LUMO
21
21
T
Ty
2
LUMOHOMO nnTbiradical character :
y = 0Fabian, J. et al. Angew. Chem. Int. Ed. 1989, 28, 677.
closed shell singlet biradical open shell
y = 1
0 < y < 1
一重項ビラジカル 閉殻 開殻
gS1
uS1
gS2
hn
hn ’
hn ’
Two-Photon Absorption of Moderate Singlet Biradical
2
2
2
2
2
4
)1(1
1
)1(1
121
)1(4
yyU
K
y
U
R
ab
BA
g ; second hyperpolarizabilityKab ; exchange integral U ; effective coulombic repulsion energyRBA ; distance between radical-sites
Kab = 0.01 0.005 0.001
yg
[a
.u.]
U = 0.1, Kab = 0.001U = 0.1
Nakano, M. et al. Phys. Rev. Lett. 2007, 99, 033001.
o-quinodimethane p-quinodimethane
Aromatic Stabilization Energy(芳香族安定化エネルギー)
90 kJ/mol
1a : R = H
1b : R = TIPS
TIPS = triisopropylsilyl
2a : R = H
2b : R =
3a : R = H
3b : R =
4a : R = H4b : R =
R
R
R R
R R
R R
Chase, D. T. et al. Angew. Chem. Int. Ed. 2011, 50, 11103.
Shimizu, A.; Tobe, Y. Angew. Chem. Int. Ed. 2011, 50, 6906.
Shimizu, A. et al. Angew. Chem. Int. Ed. 2013, 52, in press.
Aaron, G. F. et al. Org. Lett. 2013, 15, 1362-1365.
Aromatic Stabilization Energy (ASE)
Indenofluorene Derivatives1a : R = H
1b : R = TIPS
TIPS = triisopropylsilyl
2a : R = H
2b : R =
3a : R = H
3b : R =
4a : R = H4b : R =
R
R
R R
R R
R R
Chase, D. T. et al. Angew. Chem. Int. Ed. 2011, 50, 11103.
Shimizu, A.; Tobe, Y. Angew. Chem. Int. Ed. 2011, 50, 6906.
Shimizu, A. et al. Angew. Chem. Int. Ed. 2013, 52, in press.
Aaron, G. F. et al. Org. Lett. 2013, 15, 1362-1365.
S-T gap (kJ/mol) HOMO (eV) LUMO (eV) H-L gap (eV) Biradical character (%)
1a 78.5 -5.22 -2.61 2.61 30.22a 53.9 -5.11 -2.85 2.26 32.53a 6.7 -4.56 -3.22 1.34 68.34a 61.7 -5.07 -2.64 2.43 29.3
1a
2a
3a
4a
Aromatic Stabilization Energy (ASE)
indeno2,1-cfluorene
シクロオクタテトラエン (COT)
1a : R = H
1b : R = TIPS
TIPS = triisopropylsilyl
2a : R = H
2b : R =
3a : R = H
3b : R =
4a : R = H
4b : R =
R
R
R R
R R
R R
Chase, D. T. et al. Angew. Chem. Int. Ed. 2011, 50, 11103.
Shimizu, A.; Tobe, Y. Angew. Chem. Int. Ed. 2011, 50, 6906.
Shimizu, A. et al. Angew. Chem. Int. Ed. 2013, 52,1-5.
Aaron, G. F. et al. Org. Lett. 2013, 15, 1362-1365.
1D Structure
2D Structure
Hückel’s rule : Hückel's rule estimates whether a planar
( ヒュッケル則 ) ring molecule will have aromatic properties. A cyclic ring molecule follows Hückel's rule when the number of its p-electrons equals 4n+2 (n is zero or any positive integer)
aromatic(芳香族)
6(n = 1)
10(n = 2)
anti-aromatic(反芳香族)
4
non-aromatic (非芳香族)
8
4n+2 4n
18(n = 4)
COT(cyclooctatetraene ) Derivatives
820
FF
FF
FF
FF
FF
FF
FF
FF
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Zn
Ar Ar
Ar
Ar
Zn
Ar Ar
Zn
Ar
Ar
Ar =
S S
SS
S S
R R
R R
Figure 1
Zn
Einstein, F. W. B. et al.Chem. Commun.1981, 526-528.
Osuka, A. et al. J. Am. Chem. Soc.2006, 128, 4119-4127.
Iyoda, M. et al. J. Am. Chem. Soc.2010, 132, 1066-1074.
Results and Discussion
Br
F
1) n-BuLi, THF2)
3) I2
MgBr
I
1) Ac2O, aq. H2O2
2) conc. H2SO4
3) H2O, KI4) heat
I I
1) tBuLi, Et2O, -78 C2) CuCl2, -78 C
KMnO4
73% 84% 27%
pyridine, H2O
O
OH
O
HO
O
HO
O
OH
MeOHconc. H2SO4
24%(2 steps)
O
OMe
O
MeO
O
MeO
O
OMe
MesLi
48%
O
MeS
O
MeS
O
MeS
O
MeS
LiAlH4
Et2O
MeSMeS
MeS MeS
HO H H OH
HO H H OH
TFA
CH2Cl2 32%(2 steps)
MeS
MeS
MeS
MeS
DDQ
toluene r.t. 70%
MeS MeS
MeS MeS
14
5 6 7 8
9 10 11
12 13
Synthesis of 14
Hellwinkel, D. et al. Liebigs Ann. Chem. 1977, 1013-1025.
Variable-Temperature 1H NMR Measurements
H
R R
RRR =
H
D2h D4h D2h
14
S-T gap (kJ/mol)a HOMO (eV) LUMO (eV) H-L gap (eV)b Biradical character (%)c
14 23.0 -4.45 -2.92 1.53 57.9
Quantum Chemical Calculations
a S-T gap is calculated on the basis of the triplet energy that D4h symmetrical structure is optimized by UB3LYP/6-31G*and singlet energy that D2h symmetrical structure is optimized by RB3LYP/6-31G*.bH-L gap is calculated on the basis of the RB3LYP/6-31G*c Biradical character is calculated on the basis of the UHF/6-31G*//RB3LYP/6-31G*
Cristal Structure of 14
・ Thetetracyclopenta[def,jkl,pqr,vwx]tetraphenylene core is planar and the mesityl groups form a large dihedral angle of 72-88 with the backbone.
信末 俊平 , 博士論文 , 2013.
R R
RR
R R
RR
14
R =
D2h D4h
(1.33 Å)(1.54 Å) (1.20 Å)
Bond Lengthsingle bond > double bond > triple bond
Bond Length of 14
信末 俊平 , 博士論文 , 2013.
1 Å = 10-10 m
NICS Value
NICS (nucleus-independent chemical shift)The barometer that represents an effect of point’s shielding that is placed in the center of the ring. In this method, negative NICS values indicate aromaticity and positive values antiaromaticity.
D2h
+27.9
+15.5
+38.3
+24.5
D4h
+34.5+17.8
+26.0
D4h
+27.2+8.8
14
信末 俊平 , 博士論文 , 2013.
GIAO-RHF/6-31G*//RB3LYP/6-31G*
UHF/6-31G*//UB3LYP/6-31G*
GIAO-RHF/6-31G*//RB3LYP/6-31G*
UHF/6-31G*//UB3LYP/6-31G*
Conclusions・ Tetracyclopenta[def,jkl,pqr,vwx]tetraphenylene was synthesized. This compound showed biradical characters and antiaromatic because it has an inner 8p (COT) and an outer 20p conjugated cyclic systems.
R R
RR
14
・ X-ray crystallographic analysis of 14 shows that it adopts a D2h symmetric structure.
・ Synthesis of 15・ Properties of biradical character・ Effect of curved structure
Next Plan
15top view
side view
spin density
3D structure
1 2
3
4
56
7
8
9
ab
cde
f
gh
i
jk
lm
1
2 3
4
56
7
indeno2,1-cfluorene
ab
c
de
f g
h
ijk
l
mn
o
p
qrs
t
u vw
x
tetracyclopentadef , jkl, pqr, vwxtetraphenylene
o-QDM derivatives
p-QDM derivatives
Shimizu,A.,; Tobe,Y. Angew. Chem. Int. Ed. 2011, 50, 6906-6910.
Ar
Ar Ar
Ar
Ar = 4-MeOC6H4
Mes2Ge
O O
GeMes2
Ph
Ph Ph
Ph
tetraphenyl -oQDMtetraaryl-oQDM oQDM derivative
Ph
Ph Ph
Ph
n
indeno2,1 afluorene
HB0 H B0
aromatic (芳香族) anti-aromatic (反芳香族)
Application of Two-Photon Absorption①Two-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 .
②MicrofabricationStereoscopic sulptures can be made at the level of sub-micrometer by controlling the three-dimensional location of the polymerization photocurable resin .