Expanded porphyrinoids via intramolacular oxidating coupling -

synthesis and properties

Duoduo Bao &Jan Lewtak

Conjugated Porphyrin Tapes

Meso-meso singly linked arrays

Meso-meso ß-ß ß-ß triply linked arrays

Tsuda, A., Osuka, A., Adv. Mat, 2002, 14, 75-79

78%

Conjugated Porphyrin Tapes

avoiding chlorination

Up to 12, 61-90%

Tsuda, A., Osuka, A., Adv. Mat, 2002, 14, 75-79

Stability

Metal-Dependent RegioselectiveOxidative Coupling

Kamo, M., Osuka, A., Org. Lett., 2003, 5, 2079-2082

Sc(OTf)3 reacts with DDQ

Gold-Mediated Fusion Reaction of Porphyrin Dimer

TPA values

Osuka et al., Org Lett., 2006

Coming from Porphyrin-Ferrocene Dyad...

Cammidge, A.N., Berber, G., Hughes, D.L., Org. Lett., 2005, 7, 3413-3416

Absence of ferrocene

Meso- Doubly Linked Zn(II) Porphyrin Trimers

Ordinary approach – only anti

Ikeda, T., Aratani, N., Kim, D., Osuka, A., Org. Lett., 2009, 5, 3080-3083

Meso- Doubly Linked Zn(II) Porphyrin Trimers

Ikeda, T., Aratani, N., Kim, D., Osuka, A., Org. Lett., 2009, 5, 3080-3083

TPA 3<2

Pyrene-Fused Porphyrins:

Yamane, O., Sugiura, K., Miyasaka, H., Yamashita, M., Chem Lett. 2004, 33, 40-41

K/Na

A Quadruply Azulene-Fused Porphyrin

16% 16%12%

Kim, K.K., Noh, S.B., Kim, D., Osuka, A., Angew. Chem, 2006, 45, 3944-3947

63% 84% 60%

TPA cross sectionValues:9 – 340 GM10-2050 GM11-7170 GM

Expanding the Porphyrin π-System by Fusion with Anthracene

Anderson, H.L., Davis N.L.S., Pawlicki, M., Org. Lett., 2008, 10, 3945–3947

Bis-Anthracene Fused Porphyrins

Anderson, H.L., Davis N.L.S., Thompson, A.L., Org. Lett., 2010, ASAP

•IR-A: 700 nm–1400 nm (0,7 µm – 1.4 µm)•IR-B: 1400 nm–3000 nm (1.4 µm – 3 µm)•IR-C: 3000 nm–1 mm (3 µm – 1000 µm)

П-elongated porphyrin for dye-sensitized cells

Imahori, H., Matano, Y., Tanaka, M., Chem Comm., 2007, 2069-2071

larger absorptivitylow symmetry

HOMO-LUMO gap

Oxidative Rearrangement of Dispiro-Porphodimethenes

Harmjanz, M., Scott, M.J., Angew. Chem. Int. Ed., 2004, 43, 485-490

A Hexagonal Prismatic Porphyrin Array

Yoon M., Yoon Z.S, Kim, D., Osuka, A., J. Phys. Chem., 2007, 111, 9233-9239

Osuka et al.., Angew. Chem. Int. Ed, 2010, in press

Fused Tetrameric Porphyrin Sheet

Nakamura, Y.,Aratani, N., Shinokubo,H., Takagi, A., Matsumoto, T., Osuka, A., J. Am. Chem. Soc. 2006, 128, 4119-4127

Intramolecular Pd(0) catalysed coupling onortho-iodinated meso-phenyl porphyrins

Boyle, R.W., Fox., S., Chem Comm., 2004, 1322-1323 Matano, Y., Tanaka, M., Chem Lett., 2004, 37, 846-847

Summary

•Red shifted, broadened spectrum•Increasing of TPA cross section value•Nonlinear optical materials•PDT•Solar energy collecting

Challenge...

R

N N

N NR R

M

M = ???R = ???

???

FUSED CORROLE