Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2003-02-06
2004-11-02
Raymond, Richard L (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C534S015000, C534S016000, C540S121000
Reexamination Certificate
active
06812343
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a method for preparation of meso-meso, &bgr;—&bgr;, &bgr;—&bgr;, triply linked porphyrin arrays, represented by general formula 1, by oxidizing the corresponding meso-meso linked Zn(II) porphyrins, represented by general formula 2, with a selected combination of Lewis acid and quinone oxidant, and a method for preparation of meso-meso; &bgr;—&bgr;, &bgr;—&bgr;, triply porphyrin tetramers (general formula 1, n=2) from Zn(II) porphyrin monomers, represented by general formula 3 where R
1
-R
9
are substituted and especially R
2
, R
5
, and R
8
are aryl groups, and R
10
, R
11
, and R
12
are unsubstituted. The meso-meso, &bgr;—&bgr;, &bgr;—&bgr;, triply linked Zn(II) porphyrin arrays exhibit remarkable planarity and exceptionally large electronic interactions as evidenced by their absorption and electronic properties.
BACK GROUND OF THE INVENTION
Porphyrins exhibit strong absorbance in the visible region, strong fluorescence and phosphorescence, and high electric conductivity, because the HOMO-LUMO gap is relatively small. Furthermore, porphyrins have an advantage to accommodate almost all metal ions in their cavities as a ligand and such metallations and peripheral substitutions enable the tuning of optical and electrochemical properties, thus providing a variety of compounds that can fulfill the required properties when used in functional materials and devices. In nature, porphyrins are responsible for various important functions in biological processes such as oxidation-reduction reactions in metabolism, photosynthesis, and respiration. With these backgrounds, prophyrin-based molecular systems such as energy-converting functional materials and bio-mimetic catalysts have been actively developed. Recently, considerable attention has been paid to multi-porphyrin systems from a viewpoint of their application as opto-electronic material. In this line, syntheses of porphyrin polymers or oligomers bearing long, rigid, planar, and thus the exploration of extensively &pgr;-conjugated electronic systems and new devices based on the strong absorbance in the visible region, strong fluorescence and phosphorescence, and small optical HOMO-LUMO energy gap have been actively attempted.
Among these, the present inventor has reported the synthesis of directly meso-meso linked linear porphyrin polymers (consisting of 300-400 porphyrin subuints) and discrete meso-meso linked porphyrin oligomers up to a 128 mer. In addition, he also proposed the possibility of the synthesis of fused porphyrin oligomers by linking two &bgr;- and &bgr;-positions directly through oxidation of meso-meso linked porphyrin arrays.
The linear meso-meso linked porphyrin arrays have been regarded to be a promising unit for the usage as optical wire and electric molecular wire in light of rod-like structure, large electronic interactions between the neighboring porphyrin that are sufficient to induce rapid non-coherent excitation energy transfer hopping, and lack of an energy sink that blocks the energy transfer cascade long the array. These properties are apparently induced from the directly linked and perpendicular conformation of the neighboring porphyrins. The perpendicular conformation, however, leads to the disruption of &pgr;-conjugation and therefore the electric conductivity of the meso-meso linked porphyrins is only modest. When the perpendicular meso-meso linked porphyrin arrays are converted into flat and coplanar arrays by linking two&bgr;—&bgr;, &bgr;—&bgr; bonds, we may reach to extensively &pgr;-conductive porphyrin arrays that will be very promising as a molecular wire in a realistic molecular scale.
The present inventor proposed the linearly fused porphyrin arrays bearing meso-&bgr; and meso-&bgr; double linkages as a more practical candidate for molecular wire. But such arrays are not sufficient for practical applications as optical wire and molecular wire in terms of the electronic interaction and molecular size.
Therefore, the present inventor proposed a new method of preparation of meso-meso, &bgr;—&bgr;, &bgr;—&bgr; triply directly linked porphyrin arrays that extend linearly to form a tape-shape porphyrin tape (JP2000-110157 application: JP Laid Open Pub. 2001-294591). However, this synthetic protocol was only applied to the preparation of the porphyrin tapes in which the number of the porphyrin was very limited, due to concurrent peripheral &bgr;-halogenations.
The object of the present invention is to explore porphrin-based more extensively &pgr;-conjugated network which realized much longer molecular length and more electron delocalization, hence providing conjugated porphyrin arrays that will be used as optical wire and electric conducting wire.
For the use as electric wire, it is desirable to minimize the HOMO-LUMO gap as small as possible. For this purpose, extensively conjugated porphyrin arrays consisting of many porphyrins are required. Accordingly, the second object of the present invention is to establish the effective method for synthesis of conjugated porphyrin arrays of very small HOMO-LUMO gap.
In the course of these studies, the present inventor have found that a new synthetic method for converting meso-meso linked meso,meso' phenyl capped Zn(II) porphyrin oligomers to meso-meso, &bgr;—&bgr;, &bgr;—&bgr; triply directly linked Zn(II) porphyrin oligomers with quinone oxidant in the presence of suitable Lewis acid in refluxing toluene or benzonitrile solution.
DISCLOSURE OF THE INVENTION
The first one of the present invention is meso-meso, &bgr;—&bgr;,&bgr;—&bgr; triply directly linked, so-called fused porphyrin oligomers represented by general formula 1.
(wherein, R
1
-R
24
are respectively selected independently from the group consisting of hydrogen, halogen, hydroxyl group, mercapto group, amino group, nitro group, cyano group, carboxyl group, sulfonic acid group, substituted or non-substituted alkyl group, substituted or non-substituted aryl group, substituted or non-substituted alkoxy group, substituted or non-substituted aryloxy group, substituted or non-substituted alkylthio group, substituted or non-substituted arylthio group, alkylamino group, substituted or non-substituted arylamino group, substituted or non-substituted carboxylate group, substituted or non-substituted carboxylic acid amino group, substituted or non-substituted sulfonate group, substituted or non-substituted sulfonamide group, substituted or non-substituted carbonyl group, substituted or non-substituted silyl group or substituted or non-substituted siloxy group, n is an integer bigger than 2, M is 2H or a complex replaced two hydrogen atoms of porphyrin ring with metal atom selected from the group of metal atoms of A,. wherein metal atom group A is Zn, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Th, U, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Cd, Hg, Al, Ga, In, Ti, Si, Ge, Sn, Pb, As, Sb, and Bi.)
Desirably, the present invention is the above mentioned fused porphyrin oligomers, wherein in the above mentioned general formula 1, R
1
, R
4
, R
10
, R
13
, R
16
, R
22
are selected independently from phenyl groups having substituent selected independently from alkyl group or alkoxy group of carbon number 1 or more, R
7
and R
19
are respectively selected independently from the group consisting of hydrogen, halogen, hydroxyl group, mercapto group, amino group, nitro group, cyano group, carboxyl group, sulfonic acid group, substituted or non-substituted alkyl group, substituted or non-substituted aryl group, substituted or non-substituted alkoxy group, substituted or non-substituted aryloxy group, substituted or non-substituted alkylthio group, substituted or non-substituted arylthio group, alkylamino group, substituted or non-substituted arylamino group, substituted or non-substituted carboxylate group, substituted or non-substituted carboxylic acid amino group, substituted or non-substituted sulfonate group, substituted or non-substituted sulfonamide gro
Japan Science & Technology Agency
Raymond Richard L
Sherman & Shalloway
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