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Title: Covalently fixed porphyrin polymer having porphyrin metal complex substituted with coordinating hetero aromatic ring as constituting unit thereof,and method of producing the same
Abstract: A covalently linked linear porphyrin polymer represented by formula (1): ##STR00001## ##STR00002## wherein R represents an alkyl group or ##STR00003## (wherein a, b and d independently represent H, an alkyl group or aryl group); X represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H or an alkyl group), --CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S, or 2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring group; M represents an ion of metal selected from typical metals and transition metals; Q.sub.1 represents a single bond or a linear, divalent linking group; and p.sub.1 represents an integer of 2 or more.
Patent Number: 7,094,866 Issued on 08/22/2006 to Kobuke, et al.
| Inventors: |
Kobuke; Yoshiaki (Ikoma, JP), Satake; Akiharu (Ikoma, JP) | | Assignee: |
Nara Institute of Science and Technology
(Ikoma,
JP)
|
| Appl. No.:
|
10/419,767 |
| Filed:
|
April 22, 2003 |
Foreign Application Priority Data
| | | | | |
Sep 26, 2002
[JP] | | |
2002-281616 | |
|
| Current U.S. Class: |
528/395 ; 424/9.362; 424/9.61; 514/185; 514/410; 534/15; 540/145 |
| Current International Class: |
C08G 79/00 (20060101) |
| Field of Search: |
528/395 540/145 514/185,410 534/15 424/9.362,9.61
|
References Cited [Referenced By]
U.S. Patent Documents
Other References
Kofuya et al, Mercapto substituted imidazolylporphyrin metal complex monomers, their polymers, and their preparation, 2001, Jpn. Kokai Tokkyo
Koho., Chem Abstract 135: 257635. cited by examiner
.
Kofuya et al, Manufacture of polyporphyrins having imidazolylporphyrin metal complex unit, 2001, Jpn. Kokai Tokkyo Koho, Chem Abstract 135: 153257..quadrature..quadrature.. cited by examiner
.
Stibrany et al, Two modes--a structural and spectroscopic comparison, 1996, Journal of the American Chemical Society, Chem Abstract 124: 330619. cited by examiner
.
Ken-ichi Sugiura, et al. "A Mandala-Patterned Bandanna-Shaped Porphyrin Oligomer, C.sub.1244H.sub.1350N.sub.84Ni.sub.20O.sub.88, Having a Unique Size and Geometry" Chemistry Letters No. 11, pp. 1193-1194, Nov. 5, 1999. cited by other
.
Naoki Aratani, et al. "Extremely Long, Discrete meso-meso- Coupled Porphyrin Arrays" Angewandte Chemie International Edition vol. 39, No. 8, Apr. 17, 2000, pp. 1458-1462. cited by other
.
Akihiko Tsuda, et al. "Fully Conjugated Porphyrin Tapes With Electronic Absorption Bands That Reach Into Infrared" Science, vol. 293, Jul. 6, 2001, pp. 79-82. cited by other
.
Yoshiaki Kobuke, et al. "Covalent Fastening of Coordination-Organized Supramolecule" Abstract of XIIth International Symposium on Supramolecular Chemistry at Eilat, Israel, Oct. 6-11, 2002, 3 pages. cite- d by other. |
Primary Examiner: Truong; Duc
Attorney, Agent or Firm: Oblon, Spivak, McClelland, Maier & Neustadt, P.C.
Claims
What is claimed is:
1. A covalently linked linear porphyrin polymer represented by formula (1): ##STR00042## ##STR00043## wherein R represents an alkyl group or ##STR00044## (wherein a, b and d
independently represent H, an alkyl group or aryl group); X represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H or an alkyl group), --CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S, or 2H; m represents an integer of 0 to
4; n represents an integer of 0 to 6; Z represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring group; M represents an ion of metal selected from typical metals and transition metals; Q.sub.1 represents a single
bond or a linear, divalent linking group; and p.sub.1 represents an integer of 2 or more.
2. A covalently linked linear porphyrin polymer derivative represented by formula (1-1): ##STR00045## wherein R, X, Y, m, n, Z, M, Q.sub.1 and p.sub.1 have the same meaning as defined in formula (1) of claim 1; and e and f simultaneously
represent H or a hydroxyl group, or e and f are bonded to each other to form an epoxy ring together with C--C to which e and f are bonded.
3. A covalently linked cyclic porphyrin polymer represented by formula (2): ##STR00046## wherein a represents H, an alkyl group or aryl group; X represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H or an alkyl group),
--CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S, or 2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring group; M represents
an ion of metal selected from typical metals and transition metals; Q.sub.2 represents a bent divalent group; and p.sub.2 represents an integer of 3 or more.
4. A covalently linked cyclic porphyrin polymer derivative represented by formula (2-1): ##STR00047## wherein X, Y, m, n, Z, M, Q.sub.2 and p.sub.2 have the same meaning as defined in formula (2) of claim 3; and e and f simultaneously
represent H or a hydroxyl group, or e and f are bonded to each other to form an epoxy ring together with C--C to which e and f are bonded.
5. A coordination-organized linear porphyrin polymer represented by formula (3): ##STR00048## wherein a, b and d independently represent H, an alkyl group or aryl group; X represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H
or an alkyl group), --CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S, or 2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring
group; M represents an ion of metal selected from typical metals and transition metals; Q.sub.1 represents a linear divalent group; and p.sub.1 represents an integer of 2 or more.
6. A coordination-organized cyclic porphyrin polymer represented by formula (4): ##STR00049## wherein a, b and d independently represent H, an alkyl group or aryl group; X represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H
or an alkyl group), --CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S, or 2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring
group; M represents an ion of metal selected from typical metals and transition metals; Q.sub.2 represents a bent divalent group; and p.sub.2 represents an integer of 3 or more.
7. A bis-porphyrin monomer represented by formula (5): ##STR00050## wherein a, b and d independently represent H, an alkyl group or aryl group; X represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H or an alkyl group),
--CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S, or 2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z.sub.2 represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring group, alkyl
group or aryl group; M represents an ion of metal selected from typical metals and transition metals; and Q represents a single bond or a divalent linking group.
8. A covalently linked porphyrin dimer represented by formula (6): ##STR00051## wherein a represents H, an alkyl group or aryl group; X represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H or an alkyl group), --CH.sub.2-- or
a single bond; Y represents .dbd.O, .dbd.S, or 2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring group; M represents an ion of metal
selected from typical metals and transition metals; R.sup.1 represents H, an alkyl group, alkenyl group, alkynyl group, aryl group, ##STR00052## (wherein D represents a divalent group including at least one of an arylene group and alkylene group, E
represents a trivalent group including at least one of an arylene group and alkylene group, and R.sup.3 represents H or an acetyl group).
9. A covalently linked porphyrin dimer derivative represented by formula (6-1): ##STR00053## wherein X, Y, m, n, Z, M, and R.sup.1 have the same meaning as defined in formula (6) of claim 8; and e and f simultaneously represent H or a hydroxyl
group, or e and f are bonded to each other to form an epoxy ring together with C--C to which e and f are bonded.
10. A coordination-organized porphyrin dimer represented by formula (7): ##STR00054## wherein a, b and d independently represent H, an alkyl group or an aryl group; X represents --O--, --S--, >NR.sub.101 (here, R.sub.101 represents H or an
alkyl group), --CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S, or 2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring group; M represents an ion of metal selected from typical metals and transition metals; R.sup.1 represents H, an alkyl group, alkenyl group, alkynyl group, aryl group, ##STR00055## (wherein D represents a divalent group including at least one of an arylene
group and alkylene group, E represents a trivalent group including at least one of an arylene group and alkylene group, and R.sup.3 represents H or an acetyl group).
11. A porphyrin metal complex monomer represented by formula (8): ##STR00056## wherein R represents ##STR00057## (wherein a, b and d independently represent H, an alkyl group or aryl group); X represents --O--, --S--, >NR.sub.101 (wherein
R.sub.101 represents H or an alkyl group), --CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S, or 2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z.sub.2 represents a five- or six-membered, nitrogen-containing,
coordinating hetero aromatic ring group, an alkyl group or aryl group; M.sub.2 represents an ion of metal selected from typical metals and transition metals; R.sup.1 represents H, an alkyl group, alkenyl group, alkynyl group, aryl group, ##STR00058##
(wherein D represents a divalent group including at least one of an arylene group and alkylene group, E represents a trivalent group including at least one of an arylene group and alkylene group, and R.sup.3 represents H or an acetyl group).
12. A method of producing a covalently linked linear porphyrin polymer represented by formula (1): ##STR00059## wherein R represents an alkyl group or ##STR00060## (wherein a, b and d independently represent H, an alkyl group or aryl group); X
represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H or an alkyl group), --CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S, or 2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z represents a five-
or six-membered, nitrogen-containing, coordinating hetero aromatic ring group; M represents an ion of metal selected from typical metals and transition metals; Q.sub.1 represents a single bond or a linear, divalent linking group; and p.sub.1
represents an integer of 2 or more comprising: subjecting the coordination-organized linear polymer represented by formula (3) according to claim 5 to a cyclization metathesis reaction in the presence of Grubbs catalyst.
13. A method of producing a covalently linked linear porphyrin polymer derivative represented by formula (1-1): ##STR00061## wherein R, X, Y, m, n, Z, M, Q.sub.1 and p.sub.1 have the same meaning as defined in formula (1) of claim 1; and e and
f simultaneously represent H or a hydroxyl group, or e and f are bonded to each other to form an epoxy ring together with C--C to which e and f are bonded comprising: (a) hydrogenating the covalently linked linear porphyrin polymer represented by formula
(1) according to claim 1 in the presence of a metal catalyst to obtain the covalently linked linear porphyrin polymer derivative represented by formula (1-1), provided that e and f of formula (1-1) each represents H; (b) oxidizing the covalently linked
linear porphyrin polymer represented by formula (1) according to claim 1 in the presence of a catalyst to obtain the covalently linked linear porphyrin polymer derivative represented by formula (1-1), provided that e and f of formula (1-1) each
represents a hydroxy group; or (c) oxidizing the covalently linked linear porphyrin polymer represented by formula (1) according to claim 1, optionally in the presence of a catalyst, to obtain the covalently linked linear porphyrin polymer derivative
represented by formula (1-1), provided that e and f of formula (1-1) are bonded together to form an epoxy ring together with C--C to which they attach.
14. A method of producing a covalently linked cyclic porphyrin polymer represented by formula (2): ##STR00062## wherein a represents H, an alkyl group or aryl group; X represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H or
an alkyl group), --CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S, or 2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring
group; M represents an ion of metal selected from typical metals and transition metals; Q.sub.2 represents a bent divalent group; and p.sub.2 represents an integer of 3 or more comprising: subjecting the coordination-organized cyclic porphyrin polymer
represented by formula (4) according to claim 6 to a cyclization metathesis reaction in the presence of Grubbs catalyst.
15. A method of producing a covalently linked cyclic porphyrin polymer derivative represented by formula (2-1): ##STR00063## wherein X, Y, m, n, Z, M, Q.sub.2 and p.sub.2 have the same meaning as defined in formula (2) of claim 3; and e and f
simultaneously represent H or a hydroxyl group, or e and f are bonded to each other to form an epoxy ring together with C--C to which e and f are bonded comprising: (a) hydrogenating the covalently linked cyclic porphyrin polymer represented by formula
(2) according to claim 3 in the presence of a metal catalyst to obtain the covalently linked cyclic porphyrin polymer derivative represented by formula (2-1), provided that e and f of formula (2-1) each represents H; (b) oxidizing the covalently linked
cyclic porphyrin polymer represented by formula (2) according to claim 3 in the presence of a catalyst to obtain the covalently linked cyclic porphyrin polymer derivative represented by formula (2-1), provided that e and f of formula (2-1) each
represents a hydroxy group; or (c) oxidizing the covalently linked cyclic porphyrin polymer represented by formula (2) according to claim 3, optionally in the presence of a catalyst, to obtain the covalently linked cyclic porphyrin polymer derivative
represented by formula (2-1), provided that e and f of formula (2-1) are bonded together to form an epoxy ring together with C--C to which they attach.
16. A method of producing (a) a coordination-organized linear porphyrin polymer represented by formula (3): ##STR00064## wherein a, b and d independently represent H, an alkyl group or aryl group; X represents --O--, --S--, >NR.sub.101
(wherein R.sub.101 represents H or an alkyl group), --CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S, or 2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z represents a five- or six-membered, nitrogen-containing,
coordinating hetero aromatic ring group; M represents an ion of metal selected from typical metals and transition metals; Q.sub.1 represents a linear divalent group; and p.sub.1 represents an integer of 2 or more; comprising self-organizing the
bis-porphyrin monomer represented by formula (5) according to claim 7 in a non-polar solvent, provided that when Q in formula (5) represents a single bond or a linear, divalent group the coordination-organized linear porphyrin polymer represented by
formula (3) is obtained.
17. A method of producing a covalently linked porphyrin dimer represented by formula (6): ##STR00065## wherein a represents H, an alkyl group or aryl group; X represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H or an alkyl
group), --CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S, or 2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring group; M
represents an ion of metal selected from typical metals and transition metals; R.sup.1 represents H, an alkyl group, alkenyl group, alkynyl group, aryl group, ##STR00066## (wherein D represents a divalent group including at least one of an arylene group
and alkylene group, E represents a trivalent group including at least one of an arylene group and alkylene group, and R.sup.3 represents H or an acetyl group) comprising: subjecting the coordination-organized porphyrin dimer represented by formula (7)
according to claim 10 to a cyclization metathesis reaction in the presence of Grubbs catalyst.
18. A method of producing a covalently linked porphyrin dimer derivative represented by formula (6-1): ##STR00067## wherein X, Y, m, n, Z, M, and R.sup.1 have the same meaning as defined in formula (6) of claim 8; and e and f simultaneously
represent H or a hydroxyl group, or e and f are bonded to each other to form an epoxy ring together with C--C to which e and f are bonded comprising: (a) hydrogenating the covalently linked porphyrin dimer represented by formula (6) according to claim 8
in the presence of a metal catalyst to obtain the covalently linked porphyrin dimer derivative represented by formula (6-1), provided that e and f of formula (6-1) each represents H; (b) oxidizing the covalently linked porphyrin dimer represented by
formula (6) according to claim 8 in the presence of a catalyst to obtain the covalently linked linear porphyrin dimer derivative represented by formula (6-1), provided that e and f of formula (6-1) each represents a hydroxy group; or (c) oxidizing the
covalently linked linear porphyrin dimer represented by formula (6) according to claim 8, optionally in the presence of a catalyst, to obtain the covalently linked linear porphyrin dimer derivative represented by formula (6-1), provided that e and f of
formula (6-1) are bonded together to form an epoxy ring together with C--C to which they attach.
19. A method of producing a coordination-organized porphyrin dimer represented by formula (7): ##STR00068## wherein a, b and d independently represent H, an alkyl group or an aryl group; X represents --O--, --S--, >NR.sub.101 (here,
R.sub.101 represents H or an alkyl group), --CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S, or 2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z represents a five- or six-membered, nitrogen-containing,
coordinating hetero aromatic ring group; M represents an ion of metal selected from typical metals and transition metals; R.sup.1 represents H, an alkyl group, alkenyl group, alkynyl group, aryl group, ##STR00069## (wherein D represents a divalent
group including at least one of an arylene group and alkylene group, E represents a trivalent group including at least one of an arylene group and alkylene group, and R.sup.3 represents H or an acetyl group) comprising: self-organizing the porphyrin
metal complex monomer represented by formula (8) according to claim 11 in a non-polar solvent.
20. A method of producing a coordination-organized cyclic porphyrin polymer represented by formula (4): ##STR00070## wherein a, b and d independently represent H, an alkyl group or an aryl group; X represents --O--, --S--, >NR.sub.101
(wherein R.sub.101 represents H or an alkyl group), --CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S, or 2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z represents a five- or six-membered, nitrogen-containing,
coordinating hetero aromatic ring group; M represents an ion of metal selected from typical metals and transition metals; Q.sub.2 represents a bent divalent group; and P.sub.2 represents an integer of 3 or more comprising: self-organizing the
bis-porphyrin monomer represented by formula (5) according to claim 7 in a non-polar solvent, provided that when Q in formula (5) represents a bent, divalent group the coordination-organized cyclic porphyrin polymer represented by formula (4) is
obtained.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2002-281616, filed Sep. 26, 2002, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel porphyrin dimer or higher porphyrin polymer. The present invention also relates to a method of producing the same.
Further, the present invention relates to another porphyrin dimer and a porphyrin monomer which constitute the porphyrin polymer of the present invention.
The porphyrin polymer of the present invention is expected to function as an element for efficiently capturing and transferring light energy. It is contemplated that the porphyrin polymer of the present invention is applied to an artificial
photosynthesis element and an organic solar battery. Porphyrin is also known to function as a light-induced electron transfer element. Therefore, it is expected that the porphyrin polymer of the present invention can be applied to a light/electron
element of a molecular size.
2. Description of the Related Art
Porphyrin is a cyclic tetrapyrrole in which four pyrrole nucleuses are connected with four methine groups. As porphyrin has a large conjugated system including eighteen .pi. electrons, it is expected that a porphyrin polymer can be used as a
material of molecular wire or the like. Some examples of synthesizing a porphyrin polymer have been reported.
For example, Osuka of Kyoto University and Sugiura of Tokyo Metropolitan University have reported methods of extending a porphyrin polymer chain by way of covalent bonds (K. Sugiura, H. Tanaka, T. Matsumoto, T. Kawai, Y. Sakata, Chem. Lett.
1999, 1193; N. Aratani, A. Osuka, Y. H. Kim, D. H. Jeong, D. Kim, Angew. Chem. Int. Ed. 39, 1458 (2000); and A. Tsuda and A. Osuka, Science, 293, 79 (2001)). However, each of these methods requires a synthetic process with a very large number of
steps, which is economically disadvantageous. Further, in these methods, a porphyrin polymer having up to hundreds of porphyrin units can hardly be synthesized.
The inventors of the present invention have already discovered that imidazolylporphyrin metal complexes form a coordinate bond with each other, between molecules, thereby forming a porphyrin dimer or a higher porphyrin polymer (refer to the
following reaction formulae 1 and 2, and Y. Kobuke, H. Miyaji, J. Am. Chem. Soc. 1994, 116, 4111; K. Ogawa, Y. Kobuke, Angew. Chem. Int. Ed. 2000, 39, 4070; and Japanese Patent Application KOKAI Publication No. 2001-213883, which corresponds to U.S. Pat. No. 6,429,310B1, the entire contents of which are incorporated herein by reference, and Patent Application KOKAI Publication No. 2001-253883, the entire contents of which are incorporated herein by reference, which corresponds to U.S. Ser. No.
09/802,923, filed Mar. 12, 2001). Each of these porphyrin polymers functions as an energy-transferring element and thus is expected to be applicable to a molecular electronics element.
##STR00004## ##STR00005##
The unique and advantageous feature of a porphyrin polymer constituted of imidazolylporphyrin metal complexes as its constituting units lies in that the porphyrin polymer is self-organized only by mixing imidazolylporphyrin monomers in a
non-polar solvent. Accordingly, the only material that is sufficient to synthesize porphyrin polymer is porphyrin monomers, which are the smallest constituting units (refer to the above-mentioned reaction formulae 1 and 2). As compared with the methods
of Osuka and Sugiura in which a porphyrin polymer chain is extended by way of covalent bonds, this method requires a smaller number of synthesis steps, and thus is more economical. According to the method, it is actually possible to produce an extremely
large metal complex polymer having a molecular weight of 500,000 or so, in which the metal complexes are regularly arranged. However, in this method, the porphyrin polymer extended by coordinate bonds tends to have the coordinate bond thereof cut in a
polar solvent, and there arises a problem that the medium and environment applicable to the resulting porphyrin polymer are limited to non-polar ones. This limitation significantly restricts the scope of application of the porphyrin polymer (refer to
the reaction indicated by the arrow showing the shift from right to left, of the above-mentioned reaction formula 1). Therefore, it has been desired to synthesize a stable porphyrin polymer in which the porphyrin polymer chain is extended by way of
coordinate bonds, is firmly fixed and the coordinate bonds thereof are no longer cut after the polymer formation.
BRIEF SUMMARY OF THE INVENTION
An object of the present invention is to solve the above-mentioned problems. Specifically, the object of the present invention is to provide a porphyrin polymer that can stably exist without being influenced by the surrounding environment such
as the polarity of a solvent and be easily produced, even if the degree of polymerization is relatively high.
The inventors of the present invention have discovered that the above object can be attained by using a specific bis-porphyrin derivative, the porphyrin being substituted with a coordinating hetero aromatic ring, as the constituting unit of
forming a porphyrin polymer. The bis-porphyrin derivative has a bis-form in which two molecules of a mono derivative are bonded to each other by way of a divalent linking group, each mono derivative molecule being formed by binding, to a porphyrin metal
complex, one coordinating hetero aromatic ring group and two groups each having a double bond moiety that can function for a cyclization metathesis reaction. In the porphyrin polymer of the present invention, not only a coordinate bond is formed between
the coordinating hetero aromatic ring group and the core metal, but also a covalent bond is formed between the groups each having the double bond moiety, as a result of a cyclization metathesis. Accordingly, the constituting units of the porphyrin
polymer can be more firmly fixed and the porphyrin polymer can more stably exist without being influenced by the surrounding environment such as the polarity of a solvent. Further, in the case of the porphyrin polymer of the present invention, the
chain-extension method thereof requires a smaller number of synthesis steps and thus more economical, as compared with the conventional method of extending a porphyrin polymer chain by way of covalent bonds. According to the chain-extension method of
the present invention, it is actually possible to provide an extremely large metal complex polymer having a molecular weight of 500,000 or so, in which polymer the metal complexes are regularly arranged.
Specifically, the present invention provides a porphyrin polymer as described below.
(I) The present invention provides a linear porphyrin polymer represented by the following formula (1). The porphyrin polymer represented by the formula (1) has porphyrin metal complexes each substituted with a coordinating hetero aromatic ring,
as constituting units, and the porphyrin metal complexes being fixed by covalent bonds to each other (hereinafter, the porphyrin polymer represented by the formula (1) is also referred to as "covalently linked linear polymer").
##STR00006## wherein
R represents an alkyl group or
##STR00007## (wherein a, b and d independently represent H, an alkyl group or aryl group);
X represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H or an alkyl group), --CH.sub.2-- or a single bond;
Y represents .dbd.O, .dbd.S, or 2H;
m represents an integer of 0 to 4;
n represents an integer of 0 to 6;
Z represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring group;
M represents an ion of metal selected from typical metals and transition metals;
Q.sub.1 represents a single bond or a linear, divalent linking group; and
p.sub.1 represents an integer of 2 or more.
(II) Further, the present invention also provides another linear porphyrin polymer represented by the following formula (1-1), which is a derivative of the covalently linked linear polymer of the formula (1).
##STR00008## wherein
R, X, Y, m, n, Z, M, Q.sub.1 and p.sub.1 have the same meaning as defined in the formula (1) of the above-mentioned (I); and
e and f simultaneously represent H or a hydroxyl group, or e and f are bonded to each other to form an epoxy ring together with C--C to which e and f are bonded.
(III) Furthermore, the present invention also provides a cyclic porphyrin polymer represented by the following formula (2). The cyclic porphyrin polymer represented by the formula (2) has porphyrin metal complexes each substituted with a
coordinating hetero aromatic ring, as constituting units, and the porphyrin metal complexes being fixed by covalent bonds to each other (hereinafter the cyclic porphyrin represented by the formula (2) is also referred to as "covalently linked cyclic
polymer"). The covalently linked cyclic porphyrin polymer is in a cyclic structure because the divalent group represented by -Q.sub.2- for forming the bis-form, which corresponds to the linking group (-Q.sub.1-) in the formula (1), is a bent, divalent
group.
##STR00009## wherein
a represents H, an alkyl group or aryl group;
X represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H or an alkyl group), --CH.sub.2-- or a single bond;
Y represents .dbd.O, .dbd.S, or 2H;
m represents an integer of 0 to 4;
n represents an integer of 0 to 6;
Z represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring group;
M represents an ion of metal selected from typical metals and transition metals;
Q.sub.2 represents a bent divalent group; and
p.sub.2 represents an integer of 3 or more.
(IV) Moreover, the present invention also provides another cyclic porphyrin polymer represented by the following formula (2-1), which is a derivative of the covalently linked cyclic polymer represented by the formula (2).
##STR00010## wherein X, Y, m, n, Z, M, Q.sub.2 and p.sub.2 have the same meaning as defined in the formula (2) of the above-mentioned (III); and
e and f simultaneously represent H or a hydroxyl group, or e and f are bonded to each other to form an epoxy ring together with C--C to which e and f are bonded.
(V) The covalently linked linear polymer represented by the formula (1) of the present invention may be prepared by effecting a cyclization metathesis reaction of another linear porphyrin polymer represented by the following formula (3), in the
presence of Grubbs catalyst. The linear porphyrin polymer represented by the following formula (3) has porphyrin metal complexes each substituted with a coordinating hetero aromatic ring, as constituting units, the metal complexes being bonded by way of
coordinate bonds to each other (hereinafter the porphyrin polymer represented by the formula (3) is also referred to as "coordination-organized linear polymer").
The present invention also provides the coordination-organized linear polymer represented by the formula (3), and a method of producing the covalently linked linear polymer of the formula (1) by using the coordination-organized linear polymer
represented by the formula (3).
##STR00011## wherein
a, b and d independently represent H, an alkyl group or aryl group;
X represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H or an alkyl group), --CH.sub.2-- or a single bond;
Y represents .dbd.O, .dbd.S, or 2H;
m represents an integer of 0 to 4;
n represents an integer of 0 to 6;
Z represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring group;
M represents an ion of metal selected from typical metals and transition metals;
Q.sub.1 represents a linear divalent group; and
p.sub.1 represents an integer of 2 or more.
(VI) The covalently linked cyclic polymer represented by the formula (2) may be prepared by effecting a cyclization metathesis reaction of another cyclic porphyrin polymer represented by the following formula (4), in the presence of the Grubbs
catalyst. The cyclic porphyrin polymer represented by the formula (4) has porphyrin metal complexes each substituted with a coordinating hetero aromatic ring, as constituting units, the porphyrin metal complexes being bonded by way of coordinate bonds
to each other (hereinafter the cyclic porphyrin polymer represented by the formula (4) is also referred to as "coordination-organized cyclic polymer").
The present invention also provides the coordination-organized cyclic polymer represented by the formula (4), and a method of producing the covalently linked cyclic polymer represented by the formula (2) by using the coordination-organized cyclic
polymer represented by the formula (4).
##STR00012## wherein
a, b and d independently represent H, an alkyl group or aryl group;
X represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H or an alkyl group), --CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S, or 2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z represents a
five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring group; M represents an ion of metal selected from typical metals and transition metals; Q.sub.2 represents a bent divalent group; and p.sub.2 represents an integer of 3 or
more.
(VII) The coordination-organized linear polymer represented by the formula (3) and the coordination-organized cyclic polymer represented by the formula (4) can be prepared from bis-porphyrin monomer represented by the following formula (5). The
monomer represented by the formula (5) comprises two porphyrins each substituted with a coordinating hetero aromatic ring, the porphyrins being boned by a cross-liking group.
The present invention provides the bis-porphyrin monomer represented by the following formula (5), as well as a method of producing the coordination-organized linear polymer represented by the formula (3) and the coordination-organized cyclic
polymer represented by the formula (4) by self-organizing the bis-porphyrin monomer represented by the following formula (5), in a non-polar solvent. In this case, when a single bond or a linear, divalent linking group is used as the linking group
represented by -Q- in the formula (5), the coordination-organized linear polymer represented by the formula (3) is obtained. Alternatively, when a bent, divalent group is used as the linking group represented by -Q- in the formula (5), the
coordination-organized cyclic polymer represented by the formula (4) is obtained.
##STR00013## wherein a, b and d independently represent H, an alkyl group or aryl group; X represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H or an alkyl group), --CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S, or
2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z.sub.2 represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring group, alkyl group or aryl group; M represents an ion of metal selected from
typical metals and transition metals; and
Q represents a single bond or a divalent linking group.
(VIII) Further, the present invention also provides a porphyrin dimer represented by the following formula (6). The dimer represented by the formula (6) comprises two porphyrins each substituted with a coordinating hetero aromatic ring, the
porphyrins being fixed by covalent bonds to each other (hereinafter the dimer represented by the formula (6) is also referred to as "covalently linked dimer".
##STR00014## wherein a represents H, an alkyl group or aryl group; X represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H or an alkyl group), --CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S, or 2H; m represents an
integer of 0 to 4; n represents an integer of 0 to 6; Z represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring group; M represents an ion of metal selected from typical metals and transition metals; R.sup.1 represents
H, an alkyl group, alkenyl group, alkynyl group, aryl group,
##STR00015## (wherein D represents a divalent group including at least one of an arylene group and alkylene group, E represents a trivalent group including at least one of an arylene group and alkylene group, and R.sup.3 represents H or an
acetyl group).
(IX) Further, the present invention also provides another covalently linked dimer represented by the following formula (6-1), which is a derivative of the covalently linked dimer represented by the formula (6).
##STR00016## wherein X, Y, m, n, Z, M, and R.sup.1 have the same meaning as defined in the formula (6) of the above-mentioned (VIII); and e and f simultaneously represent H or a hydroxyl group, or e and f are bonded to each other to form an
epoxy ring together with C--C to which e and f are bonded.
(X) The covalently linked dimer represented by the above formula (6) may be obtained by effecting a cyclization metathesis reaction of another porphyrin dimer represented by the following formula (7), in the presence of the Grubbs catalyst. The
dimer represented by the formula (7) comprises two porphyrins each substituted with a coordinating hetero aromatic ring, the porphyrins being fixed by coordinate bonds to each other (hereinafter the dimer represented by the formula (7) is also referred
to as "coordination-organized dimer".
The present invention also provides the coordination-organized dimer represented by formula (7), and a method of producing the covalently linked dimer of the formula (6) by using the coordinately boned dimer represented by the formula (7).
##STR00017## wherein a, b and d independently represent H, an alkyl group or an aryl group; X represents --O--, --S--, >NR.sub.101 (here, R.sub.101 represents H or an alkyl group), --CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S,
or 2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring group; M represents an ion of metal selected from typical metals and transition
metals; R.sup.1 represents H, an alkyl group, alkenyl group, alkynyl group, aryl group,
##STR00018## (wherein D represents a divalent group including at least one of an arylene group and alkylene group, E represents a trivalent group including at least one of an arylene group and alkylene group, and R.sup.3 represents H or an
acetyl group).
(XI) The present invention also provides a porphyrin metal complex monomer represented by the following formula (8), the porphyrin metal complex being substituted with a coordinating hetero aromatic ring, and a method of producing the
coordination-organized diner represented by the formula (7) by using the monomer represented by the formula (8).
##STR00019## wherein R represents an alkyl group or
##STR00020## (wherein a, b and d independently represent H, an alkyl group or aryl group); X represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H or an alkyl group), --CH.sub.2-- or a single bond; Y represents .dbd.O, .dbd.S,
or 2H; m represents an integer of 0 to 4; n represents an integer of 0 to 6; Z.sub.2 represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring group, an alkyl group or aryl group; M.sub.2 represents an ion of metal
selected from typical metals and transition metals; R.sup.1 represents H, an alkyl group, alkenyl group, alkynyl group, aryl group,
##STR00021## (wherein D represents a divalent group including at least one of an arylene group and alkylene group, E represents a trivalent group including at least one of an arylene group and alkylene group, and R.sup.3 represents H or an
acetyl group).
Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention
may be realized and obtained by means of the instrumentalities and combinations particularly pointed out hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows ultraviolet-visible absorption spectra of the compound A-11a. In the graph, the solid line, thick line and dotted line represent the case in which chloroform methanol/chloroform (100:1) and pyridine were used, respectively, as a
solvent;
FIG. 2 shows GPC chromatogram of the compound B-7 (Column: JAIGEL-2.5HA manufactured by Japan Analytical Industry Co., Ltd., Eluent: chloroform, Flow rate: 1.2 mL/min). In the graph, the broad peak (the maximum peak at 9.6 min.) represents the
result of the compound B-7. The sharp peaks observed at the retention time of 8.6 min. (molecular weight: 44,000), of 9.6 min. (MW: 21,000), of 11.2 min. (MW: 7,000), of 12.0 minutes (MW: 3,790), of 12.6 min. (MW: 2,090), and of 13.5 min. (MW: 920),
respectively, are shown in a manner that the result obtained by analyzing the polystyrene reference material in the same condition is overlapped thereon;
FIG. 3 shows MALDI-TOF mass spectrometry spectrum (matrix: dithranol) of the compound B-7. In the graph, the molecular weight-peaks at 1,346, 2,698, 4,039, 5,388 and 6,742 correspond to fragment peaks of porphyrin unit number 2, 4, 6, 8, and 10,
respectively, at which carbon-carbon triple bond of polyacetylene has been cut in the measurement condition;
FIG. 4 shows ultraviolet-visible absorption spectrum of the polymer B-7 (Solvent: chloroform);
FIG. 5 shows ultraviolet-visible absorption spectrum of the polymer B-7 (Solvent: pyridine);
FIG. 6 shows ultraviolet-visible absorption spectrum of the zinc porphyrin B-6 (Solvent: pyridine);
FIG. 7 shows GPC chromatograms of the polymer C-5 before and after re-organization (Column: JAIGEL-3HA manufactured by Japan Analytical Industry Co., Ltd., Eluent: chloroform, Flow rate: 1.2 mL/min). In the graph, the thick line and solid line
present the result obtained from the sample before and after re-organization. That is, the half-band width of chromatography representing the sample after re-organization is narrower than that of before re-organization;
FIG. 8 shows results of GPC chromatograms of the polymer C-6a and the polymer C-6b that were separation-purified after the metathesis reaction (Column: JAIGEL-3HA manufactured by Japan Analytical Industry Co., Ltd., Eluent: chloroform, Flow rate:
1.2 mL/min). In the graph, the thick line, solid line and dotted line represent C-6a (hexamer), C-6b (pentamer) and the sample before being separation-purified, respectively;
FIG. 9 shows ultraviolet-visible absorption spectra of the compound C-6a. In the graph, the thick line and solid line present the case using chloroform and pyridine, respectively, as a solvent;
FIG. 10 shows ultraviolet-visible absorption spectra of the compound C-6b. In the graph, the thick line and solid line represent the case using chloroform and pyridine, respectively, as a solvent;
FIG. 11 shows a measurement result of MALDI-TOF mass spectrometry spectrum (matrix: dithranol) of the compound C-6a; and
FIG. 12 shows MALDI-TOF mass spectrometry spectrum (matrix: dithranol) of the compound C-6b.
DETAILED DESCRIPTION OF THE INVENTION
First, a covalently linked linear polymer represented by the formula (1) of the present invention will be described in detail.
In the formula (1), R represents an alkyl group or
##STR00022##
wherein a, b and d independently represent H, an alkyl group or aryl group.
In the present specification, an "alkyl group" means a normal, branched or cyclic monovalent aliphatic group. When any substituent other than the groups a, b and d is an alkyl group, hereinafter, the alkyl group has the same meaning. An "aryl
group" represents a monovalent aromatic hydrocarbon group, which may be either monocyclic or a condensed ring constituted of at least two rings. When any substituent other than the groups a, b and d is an aryl group, the aryl group has the same meaning. The alkyl group and the aryl group may have a substituent group, if possible. The same can be applied to the alkyl and aryl groups other than those represented by the groups a, b and d.
The number of carbon atoms of the alkyl group represented by a, b and d is generally 1 to 8, and preferably 1 to 2. However, the number of carbon atoms is not particularly limited to these, and may be selected in consideration of: whether or not
the double bond between the carbon atom to which a is bonded and the carbon atom to which b and d are bonded can function for the cyclization metathesis reaction; how easily the raw material for the polymer represented by the formula (1) can be
synthesized; the function/capacity which the product is expected to have; and the like.
The number of carbon atoms of the aryl group represented by a, b and d is generally 6 to 20 (e.g., phenyl, naphthyl, anthracenyl, pyrenyl and naphthacenyl), and preferably 6 to 10. However, the number of the carbon atoms is not particularly
limited to these, and may be selected in a viewpoint similar to those described above for the alkyl group.
In the formula (1), the alkyl group represented by R has the same meaning as described with respect to the aforementioned a, b and d.
In the formula (1), X represents --O--, --S--, >NR.sub.101 (wherein R.sub.101 represents H or an alkyl group), --CH.sub.2-- or a single bond.
The number of carbon atoms of the alkyl group represented by R.sub.101 is preferably 1 to 4 or so, although the number is not particularly limited to these.
In the formula (1), X is preferably --O--, in consideration of easiness of synthesis of the raw material compound, the function that the product is expected to have, and the like.
In the formula (1), Y represents .dbd.O, .dbd.S or 2H. Herein, the expression that "Y represents 2H" indicates that two hydrogen atoms are bonded, by single bond, to the carbon atom to which Y is bonded.
Y is preferably .dbd.O, in consideration of easiness of synthesis of the raw material compound, the function that the product is expected to have, and the like.
In the formula (1), m represents an integer of 0 to 4. m is preferably 1, in consideration of easiness of synthesis of the raw material compound, the function that the product is expected to have, and the like.
In the formula (1), n represents an integer of 0 to 6. n is preferably 2, in consideration of easiness of synthesis of the raw material compound, the function that the product is expected to have, and the like.
In the formula (1), Z represents a five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring group. The type of the "five- or six-membered, nitrogen-containing, coordinating hetero aromatic ring group" is not particularly
restricted, as long as the hetero cycle including at least one nitrogen atom and has aromaticity. The hetero cycle represented by Z may include oxygen atom, sulfur atom or the like as a hetero atom other than nitrogen. In a case in which the
nitrogen-containing, coordinating hetero aromatic ring group has structural isomers thereof, the group also represents these structural isomers.
A five-membered, nitrogen-containing, coordinating hetero aromatic ring group and a six-membered, nitrogen-containing, coordinating hetero aromatic ring group include following imidazolyl, oxazolyl and thiazolyl groups, and pyridyl group, but the
hetero aromatic group is not limited to these.
##STR00023##
In the above imidazolyl group, the number of carbon atoms of the alkyl group represented by R.sup.2 is generally 1 to 10, and preferably 1 or so, in consideration of easiness of synthesis of the raw material compound, the function that the
product is expected to have, and the like.
In the formula (1), Z preferably represents imidazolyl groups, in consideration of the strength of bond between Z and the core metal of the porphyrin metal complex.
In the formula (1), M represents an ion of metal selected from typical metals and transition metals. Herein, the "typical metals" represent metals of 1A, 2A, 2B, 3B to 7B, and 0 groups in the long form of the periodic table. More specifically,
the typical metals include Mg, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi and the like. On the other hand, the "transition metals" represent metals of 3A to 7A, 8 and 1B groups in the long form of the periodic table. More specifically,
the transition metals represent Sc, Y, lanthanoid (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au and the like. The valence number of these metals
is generally II- or III-valent, although the valence number of these metals is not particularly limited as long as the metal can serve as the core metal of a porphyrin metal complex.
The type of the metal ion M is not particularly restricted, as long as M is capable of forming coordinate bond between itself and the above-mentioned Z. However, M is preferably Zn, Mg, Co, Fe or the like, in consideration of the reactivity, the
strength of the bond, the function that the product is expected to have, and the like.
In the formula (1), Q.sub.1 represents a single bond or a linear, divalent linking group. The linear, divalent linking group may be selected, in consideration of the function that the resulting product is expected to have (e.g., conductivity of
electron/energy, the strength with which the porphyrin rings are bonded to each other, the capacity of maintaining the steric configuration, and the like).
Herein, the linear, divalent linking group includes: (a) a divalent linking group whose connecting bonds at both ends thereof are aligned on the same line; or (b) a divalent linking group whose connecting bonds at both ends thereof are aligned in
parallel with each other. Here, the expression that the connecting bonds at both ends of the divalent linking group are "aligned on the same line" does not necessarily mean that the connecting bonds are aligned on the same, geometrically perfect line.
Similarly, the expression that the connecting bonds at both ends of the divalent linking group are "aligned in parallel with each other" does not necessarily mean that the connecting bonds are aligned in parallel with each other in the geometrically
perfect manner. Accordingly, it suffices, as long as the polymer constituted by way of the liner, divalent linking group is not cyclic, but takes on the substantially linear chain-like form as a whole. In particular, in the case in which the polymer
formed by way of the liner, divalent linking group is relatively long, the connecting bonds at both ends of the liner, divalent group need to be neither aligned on the same, geometrically perfect line nor aligned in parallel (with each other) in the
geometrically perfect manner. In this case, a chain-like polymer can reliably be formed as long as the connecting bonds at both ends of the liner, divalent group are located substantially on the same line or aligned substantially in parallel with each
other. Hereinafter, in the present specification, the state in which the connecting bonds are aligned substantially on the same line and the state in which the connecting bonds are aligned substantially in parallel with each other will simply be
referred to as "linear" and "in parallel", respectively.
Examples of the group (a) whose connecting bonds at both ends thereof are aligned on the same line include: a divalent, saturated or unsaturated aliphatic hydrocarbon group {e.g., alkylene group having 1 3 carbon atoms (e.g., --CH.sub.2--),
--C.ident.C--}; a divalent, saturated or unsaturated hydrocarbon ring group {e.g., a monocycle or a condensed ring having 3 20 carbon atoms (e.g., 1,3-cyclobutylene (in trans form), 1,4-phenylene, 2,7-pyrenylene)}; a divalent, saturated or unsaturated
hetero cyclic group {e.g., a six-membered hetero cycle containing at least one N, S, O, P atom or the like as a hetero atom (such as 2,5-pyridine)}; and a combination of at least two of the aforementioned divalent groups. When at least two of the
aforementioned divalent groups are combined, the groups may be either of the same type (the resulting structure is what is called a bis structure) or of different types. Combining the groups of the same type is preferable, in terms of making the
synthesis of the raw material compound easy. Further, when at least two of the aforementioned divalent groups are combined, these divalent groups may be bonded by way of a group whose connecting bonds at both ends thereof are aligned on the same line,
such as --O-- and --C(.dbd.O)--. Still further, the divalent groups may be bonded by way of any linking group, as long as the connecting bonds of both ends of the linking group represented by Q.sub.1 are eventually aligned on the same line.
Examples of the group (b) whose connecting bonds at both ends thereof are aligned in parallel with each other include: a divalent, saturated or unsaturated normal hydrocarbon group {e.g., normal alkyl groups having 3 5 carbon atoms (such as
n-propylene), --C.dbd.C-- (in trans form)}; a divalent, aromatic hydrocarbon ring group {e.g., condensed rings having approximately 10 20 carbon atoms (e.g., 2,6-naphthylenyl and 1,6-pyrenylene)}; and the like.
Further, the aforementioned group (a) whose connecting bonds at both ends thereof are aligned on the same line may be combined with the aforementioned group (b) whose connecting bonds at both ends thereof are aligned in parallel with each other,
as long as the connecting bonds of the thus formed divalent group are eventually aligned on the same line or aligned in parallel with each other.
Specific examples of the divalent linking group whose connecting bonds at both ends thereof are: (a) aligned on the same line or (b) aligned in parallel with each other are described below. It should be noted, however, that the group represented
by Q.sub.1 is not limited to these.
##STR00024## ##STR00025##
In the formula (1), Q.sub.1 is preferably a single bond or alkynylene group represented by the formula: (--C.ident.C--).sub.n, wherein n represents an integer of 1 to 3), in consideration of the strength of the bond, stability, and easiness of
the synthesis of the raw material.
In the formula (1), p.sub.1 represents an integer of 2 or more. The value of p.sub.1 may be selected, in an appropriate manner, according to the application or the like of the covalently linked linear polymer of the present invention. There
exists no particular upper limit of the p.sub.1 value. Currently, it is possible to produce a covalently linked linear polymer in which the p.sub.1 value is approximately up to 100.
In the formula (1), the wavy line drawn from the substituent group X represents the presence of both trans and cis isomers (similarly, a wavy line found in other formulae indicates the presence of both trans and cis isomers). In a case in which
there exist at least two sites at which trans/cis steric isomerism can occur in a covalently linked linear polymer, as is the case with the polymer represented by the formula (1), the a covalently linked linear polymer will possibly have various steric
isomers thereof, according to the combination of cis/trans structure at the sites at which trans/cis steric isomerism occurs. In the present invention, the covalently linked linear polymer of the formula (1) includes all of the individual isomers as
described above and mixtures thereof, which are theoretically possible (hereinafter, the same principal can be applied to any other compounds represented by other formulae, when isomers thereof can exist).
Further, the plural same letters employed in the formula (1) may be the same group or different. However, in consideration of easiness of the synthesis process, it is preferable that these plural same letters represent the same group or atom
(the same principal as this may be applied to other formulae, too).
The linear polymer represented by the formula (1-1) of the present invention is a derivative of a covalently linked linear polymer of the formula (1), in which the covalent bond (the alkene portion) in the repetitive unit portion of the formula
(1) shown below:
##STR00026## is replaced with an alkane to become:
##STR00027## is replaced with hydroxy to become:
##STR00028## is replaced with epoxy to become:
##STR00029##
Next, a covalently linked cyclic polymer represented by the formula (2) of the present invention will be described in detail.
The covalently linked cyclic polymer represented by the formula (2) of the present invention is characterized in that the bridging group represented by Q.sub.2, which links two porphyrins is a divalent group in a bent form, and not linear as is
the linking group represented by Q.sub.1 in the formula (1).
In the formula (2), the divalent linking group in a bent form may be selected in consideration of the function that the resulting product is expected to have (e.g., conductivity of electron or energy, the strength with which porphyrin rings are
bonded to each other, the capacity of maintaining the steric configuration, and the like), as is the case with selection of Q.sub.1 of the formula (1).
The divalent group in a bent form, represented by Q.sub.2, represents a divalent group whose connecting bonds at both ends thereof are neither aligned on the same line nor aligned in parallel with each other, but disposed with an angle formed
therebetween. When the angle formed between the one connecting bond at one end of the divalent group and the other connecting bond at the other end of the same divalent group is in a range of 60.degree. to 145.degree. or so, a cyclic structure of the
polymer can be made easily. Examples of such a group include: an unsaturated normal hydrocarbon {e.g., those having two carbon atoms such as --C.dbd.C-- (cis) and the like}; a saturated or unsaturated carbon ring {e.g., monocycle or condensed rings
having 3 20 carbon atoms (such as cyclopropenylene, 1,3-phenylene, 3,6-naphthylene and the like)}; and a saturated or unsaturated heterocycle (e.g., five- or six-membered heterocycle containing at least one atom selected from N, S, O, P and the like as a
hetero atom (such as 1,3-phenyl, 3,5-pyridilene and the like)). Aromatic hydrocarbon such as benzene ring may be fused to the saturated or unsaturated heterocycle. Further, a connecting bond may extend from such fused rings.
Specific examples of the divalent linking group in a bent form are set forth below. It should be noted, however, that the group represented by Q.sub.2 is not limited to these.
##STR00030##
In the covalently linked cyclic polymer of the formula (2), a, X, Y, m, n, Z and M have the same meaning as defined in the formula (1).
In the formula (2), p.sub.2 represents an integer of 3 or more. The value of p.sub.2 may be selected, in an appropriate manner, according to the application and the like of the covalently linked cyclic polymer of the present invention. There
exists no particular upper limit of the p.sub.2 value. Theoretically, it is assumed that a covalent bond cyclic polymer whose p.sub.2 value is approximately 20 can be produced. Currently, it is possible to produce a covalent bond cyclic polymer in
which the p.sub.2 value is approximately 6.
The polymer represented by the formula (2-1) of the present invention is a derivative of the covalently linked cyclic polymer represented by the formula (2), and is the same as the polymer represented by the formula (2), except that the covalent
bond of the repeating unit portion (the alkene portion) of the formula (2) is replaced with alkane, hydroxy or epoxy (the alkane, hydroxy and epoxy are defined in the same manner as in the formula (1-1)).
Next, the coordination-organized linear polymer represented by the formula (3) and the coordination-organized cyclic polymer represented by the formula (4) will be described below.
The coordination-organized linear polymer represented by the formula (3) is the same, with regards to each substituent thereof, as the covalently linked linear polymer represented by the formula (1). However, the former is different from the
latter in that the repeating unit portion of the formula (1) does not have a covalent bond resulted from the cyclization metathesis reaction. The cyclization metathesis reaction will be described in detail later.
The coordination-organized cyclic polymer represented by the formula (4) is the same, with regards to each substitue
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