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

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

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

  2. Contents Introduction -Singlet biradical 2. Results and discussion 3. Conclusion 4. Next plan

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. Aromatic Stabilization Energy (ASE)

  8. 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

  9. 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)

  10. 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.

  11. Results and Discussion

  12. Synthesis of 14 Hellwinkel,D. et al. Liebigs Ann. Chem. 1977, 1013-1025.

  13. Variable-Temperature 1H NMR Measurements H

  14. 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*

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Next Plan 3D structure side view top view ・Synthesis of 15 ・Properties of biradicalcharacter ・Effect of curved structure spin density

  20. o-QDM derivatives p-QDM derivatives Shimizu,A.,; Tobe,Y. Angew. Chem. Int. Ed.2011, 50, 6906-6910.

  21. 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 .

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