Expanded porphyrinoids via intramolacular oxidating coupling - synthesis and properties Duoduo Bao &...
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Transcript of Expanded porphyrinoids via intramolacular oxidating coupling - synthesis and properties Duoduo Bao &...
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
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