Synthesis and Properties of Tetracyclopenta def, jkl, pqr, vwx tetraphenylene Tobe Lab. Kenta Ohtsuka.

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 .