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Synthesis and Properties of T etracyclopenta  def, jkl , pqr , vwx  tetraphenylene. Tobe Lab. Kenta Ohtsuka. Contents. Introduction -Singlet biradical 2. Results and discussion 3. Conclusion 4. Next plan. Singlet Biradical. closed shell. singlet biradical. open shell.

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slide1

Synthesis and Properties of Tetracyclopentadef, jkl, pqr, vwxtetraphenylene

Tobe Lab.

Kenta Ohtsuka

slide2

Contents

Introduction

-Singlet biradical

2. Results and discussion

3. Conclusion

4. Next plan

slide3

Singlet Biradical

closed shell

singlet biradical

open shell

一重項ビラジカル

閉殻

開殻

y = 1

0 < y < 1

Fabian, J. et al. Angew. Chem. Int. Ed.1989, 28, 677.

y = 0

biradical character :

nHOMO, nLUMO; occupation numbers of HOMO or LUMO

UHF/6-31G*//UB3LYP/6-31G* and Yamaguchi scheme

Yamaguchi, K. Chem. Phys. Lett. 1975, 33, 330.

slide4

Two-Photon Absorption of Moderate Singlet Biradical

Kab= 0.01

0.005

0.001

hn ’

g [a.u.]

hn

hn ’

y

U = 0.1, Kab = 0.001

U = 0.1

g ; second hyperpolarizability

Kab ; exchange integral

U ; effective coulombic repulsion energy

RBA ; distance between radical-sites

Nakano, M. et al. Phys. Rev. Lett.2007, 99, 033001.

slide5

Aromatic Stabilization Energy (ASE)

Shimizu, A.; Tobe, Y. Angew. Chem.

Int. Ed. 2011, 50, 6906.

Chase, D. T. et al. Angew. Chem.

Int. Ed. 2011, 50, 11103.

Shimizu, A. et al.Angew. Chem. Int. Ed.

2013, 52, in press.

Aaron, G. F. et al. Org. Lett.

2013, 15, 1362-1365.

p-quinodimethane

o-quinodimethane

slide6

IndenofluoreneDerivatives

Shimizu, A.; Tobe, Y. Angew. Chem.

Int. Ed. 2011, 50, 6906.

Chase, D. T. et al. Angew. Chem.

Int. Ed. 2011, 50, 11103.

Shimizu, A. et al.Angew. Chem. Int. Ed.

2013, 52, in press.

Aaron, G. F. et al. Org. Lett.

2013, 15, 1362-1365.

slide8

1D Structure

Shimizu, A.; Tobe, Y. Angew. Chem.

Int. Ed. 2011, 50, 6906.

Chase, D. T. et al. Angew. Chem.

Int. Ed. 2011, 50, 11103.

Shimizu, A. et al.Angew. Chem. Int. Ed.

2013, 52,1-5.

Aaron, G. F. et al. Org. Lett.

2013, 15, 1362-1365.

2D Structure

slide9

Hückel’srule :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)

slide10

COT(cyclooctatetraene ) Derivatives

Iyoda, M. et al. J. Am. Chem. Soc.

2010, 132, 1066-1074.

Einstein, F. W. B. et al.

Chem. Commun.

1981, 526-528.

Osuka, A. et al. J. Am. Chem. Soc.

2006, 128, 4119-4127.

slide12

Synthesis of 14

Hellwinkel,D. et al. Liebigs Ann. Chem. 1977, 1013-1025.

slide14

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*

slide15

Cristal Structure of 14

・Thetetracyclopenta[def,jkl,pqr,vwx]tetraphenylenecore 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.

slide16

Bond Length of 14

Bond Length

single bond > double bond > triple bond

(1.54Å)

(1.33 Å)

(1.20 Å)

1 Å = 10-10 m

信末 俊平, 博士論文, 2013.

slide17

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.

GIAO-RHF/6-31G*//

RB3LYP/6-31G*

GIAO-RHF/6-31G*//

RB3LYP/6-31G*

UHF/6-31G*//

UB3LYP/6-31G*

UHF/6-31G*//

UB3LYP/6-31G*

信末 俊平, 博士論文, 2013.

slide18

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.

・X-ray crystallographic analysis of 14shows that it adopts

a D2h symmetric structure.

slide19

Next Plan

3D structure

side view

top view

・Synthesis of 15

・Properties of biradicalcharacter

・Effect of curved structure

spin density

slide23

o-QDM derivatives

p-QDM derivatives

Shimizu,A.,; Tobe,Y. Angew. Chem. Int. Ed.2011, 50, 6906-6910.

slide25

Application of Two-Photon Absorption

①Two-photon Photodynamic Therapy

By using two-photon absorption, long-wavelength light that isless 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

Stereoscopicsulptures can be made at the level of sub-micrometer by controlling the three-dimensional location of the polymerization photocurable resin .