Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta...
-
Upload
theodore-christopher-jefferson -
Category
Documents
-
view
229 -
download
0
Transcript of Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta...
![Page 1: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/1.jpg)
Synthesis and Properties of Tetracyclopenta def, jkl, pqr,
vwxtetraphenylene
Tobe Lab.Kenta Ohtsuka
![Page 2: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/2.jpg)
Contents
1. Introduction -Singlet biradical
2. Results and discussion
3. Conclusion
4. Next plan
![Page 3: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/3.jpg)
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
![Page 4: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/4.jpg)
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.
![Page 5: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/5.jpg)
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)
![Page 6: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/6.jpg)
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
![Page 7: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/7.jpg)
1a
2a
3a
4a
Aromatic Stabilization Energy (ASE)
![Page 8: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/8.jpg)
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
![Page 9: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/9.jpg)
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)
![Page 10: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/10.jpg)
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.
![Page 11: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/11.jpg)
Results and Discussion
![Page 12: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/12.jpg)
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.
![Page 13: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/13.jpg)
Variable-Temperature 1H NMR Measurements
H
R R
RRR =
H
![Page 14: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/14.jpg)
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*
![Page 15: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/15.jpg)
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.
![Page 16: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/16.jpg)
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
![Page 17: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/17.jpg)
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*
![Page 18: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/18.jpg)
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.
![Page 19: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/19.jpg)
・ Synthesis of 15・ Properties of biradical character・ Effect of curved structure
Next Plan
15top view
side view
spin density
3D structure
![Page 20: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/20.jpg)
![Page 21: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/21.jpg)
![Page 22: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/22.jpg)
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
![Page 23: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/23.jpg)
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
![Page 24: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/24.jpg)
HB0 H B0
aromatic (芳香族) anti-aromatic (反芳香族)
![Page 25: Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.](https://reader036.fdocuments.us/reader036/viewer/2022062300/56649ccd5503460f94997b41/html5/thumbnails/25.jpg)
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 .