Tobe Lab. Kenta Ohtsuka

1. Structures and Properties of Bowl-Ｓhaped Compounds Tobe Lab. Kenta Ohtsuka

2. 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

3. Singlet Biradical Shimizu, A.; Tobe, Y. Angew. Chem. Int. Ed. 2011, 50, 6906. Chase, D. T. et al. Angew. Chem. Int. Ed. 2011, 50, 11103 -11106. p-quinodimethane o-quinodimethane

4. Aromatic Stabilization Energy (ASE) 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.

5. Properties derived from singlet biradical 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. hn’ hn Kab= 0.01 0.005 0.001 hn’ g [a.u.] g ; second hyperpolarizability Kab ; exchange integral U ; effective coulombic repulsion energy RBA ; distance between radical-sites y rubrene 67 GM GM = 10−50 cm4 s photon−1 molecule−1 >1100 GM

6. Motivation Aaron, G. F. et al. Org. Lett. 2013, 15, 1362-1365. 2D 3D

7. Motivation

8. Motivation

9. Bucky Bowls the generic name of the bowl-shaped conjugated compounds correspondingto substructure of fullerenes or the cap structure of the carbon nanotube. carbonnanotube Imamure, K.; Takamiya, K. et al. Chem. Commun., 1999, 1859-1860.

10. Corannulene Corannulene is a polycyclic aromatic hydrocarbon with chemical formula C20H10. The compound consists of a cyclopentanering fused by five benzene rings. It is of scientific interest because it can be considered as a fragment of fullerene.

11. Synthesis of Corannulene Anna, M. B. et al. Org. Process Res. Dev. 2012, 16, 664-676.

12. Sumanene • sumanene is a polycyclic aromatic hydrocarbon and of • scientific interest because the compound can be • considered a fragment of fullerene. • The core of sumaneneis a benzene ring and the • periphery consists of six-membered rings and five- • membered rings. • Sumanene has three sp3 hybridized carbon atoms at the • benzylic positions.

13. Synthesis of Sumanene Sakurai, H.; Daiko, T. et al. J. Am. Chem. Soc. 2005, 127, 11580-11581.

14. Crystal Packing of Sumanene 3.86Å 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.

15. 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 2D Structure POAV = 0 POAV = 0 Amaya, T.; Sakane, H. et al. Pure Appl. Chem. 2010, 82, 969–978.

16. Corannulene Sumanene Fullerene Hindy, E. B. et al. J. Am. Chem. Soc. 2002, 124, 8870-8875. BD = 0.89 Å BD = 1.15 Å Andrzej, S. et al. J. Am. Chem. Soc. 1996, 118, 339-343. 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 .

17. POAV of My Compound POAV = 5.4 POAV = 7.6 BD(Bowl Depth) of My Compound 0.84Å

18. 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. • Corannulenerepresents bowl-to-bowl inversionand 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.

19. 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.

20. 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))

21. Discussion sumanene coronene my compound

22. Discussion Corannulene My compound planar structure planar structure Bowl shaped structure bowl shaped structure

23. Conclusions ・Bucky bowls such as corannulene and sumanene showed bowl-to-bowl inversion with 8.63 kcal/mol, 16.8 kcal/mol respectivelyand my compound showed bowl- to-bowl inversion with 6.46 kcal/mol. ・POAV, BD, and the barrier for thebowl-to-bowl inversion of mycompound 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.

24. Outlook

27. Packing of Corannulene

28. 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 .