3. Porphyrin Derivatives
3-1. Doubly N-Confused Porphyrin
Doubly N-confused poprhyrin (N2CP) was synthesized from the N-confused dipyrromethane. Two isomers, cis- and trans-types, were isolated as air-stable compounds (JACS 2000, JACS 2003). Both the two isomers can stabilize high oxidation states of metal ions, such as Cu(III) and Ag(III). Reflecting the different location of the two peripheral nitrogen atoms, the trans-N2CP forms a straight type of 1-D hydrogen bonding network and the cis-N2CP forms a zigzag type of network in the solid state (Supramol. Chem. 2003, JACS 2003). Moreover, cis-N2CP-Ag(III) complex exhibitted the property of an efficient sensitizer for singlet oxygen generation (CL 2003, J. Photochem. Photobiol. A 2004).
3-2. N-Confused Calix[4]phyrin
The concept of "confusion" is also applicable to other porphyrinoids. In order to obtain nonconjugated cyclic ligands for stabilization of carbon-metal bond, dimethyl N-confused calix[4]phyrin (DMNCP) was synthesized from pyrrole, arylaldehyde, and acetone. The two methyl groups were selectively introduced into meso-position next to β-CH of the confused pyrrole, and additionally, α-CH of the confused pyrrole was oxidized to form amide-like group. DMNCP gave the Ni(II), Cu(II), and Zn(II)-complexes, and the structures were confirmed by X-ray single crystal analyses. The Cu(II) complex is the first crystallographically characterized organometallic Cu(II) complexes possessing a carbon-Cu(II) bond (ACIE 2001, Inorg. Chem. Commun. 2003).
3-3. Corrorin and Oxyindolophyrin
Corrorin was isolated as a side product of the cis-N2CP synthesis from N-confused dipyrromethane. Corrorin rearranges to a novel aromatic porphyrin analog, oxyindolphyrin by a treatment with SnCl2. The strong F－ binding property of oxyindolophyrin was demonstrated by the spectroscopic methods (JACS 2001).
3-4. Tetrapyrrolylporphyrin
By the condensation of N-alkyl-2,4-pyrroledicarbaldehyde and pyrrole, a porphyrin bearing four pyrrolyl groups at the four meso-positions was obtained (OL 2000).
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