JP3275233B2 - Poly (5,15-diaryl-substituted Zn (II) -porphyrylene) compounds and methods for their synthesis - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a poly (5,15-
Diaryl-substituted Zn (II) -porphyrylene) compound, metal-free porphyrylene compound and Zn by Mg, Ca, Sr, Ba, Sc, Y, La, C
e, Pr, Nd, Sm, Eu, Gd, Tb, Dy, H
o, 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, P
d, Pt, Cu, Ab, Au, Cd, Hg, Al, G
a, In, Tl, Si, Ge, Sn, Pb, As, S
b, the porphyrinylene compound substituted with Bi (in the present specification, the poly (5,15-
Diaryl-substituted Zn (II) -porphyrylene) compounds. ) And a method for producing the poly (5,15-diaryl-substituted Zn (II) -porphyrinylene) compound.

[0002]

2. Description of the Related Art Linear π-conjugated polymers and oligomers have attracted attention as promising materials in the fields of electronic materials, optical devices, sensors, and solar energy conversion materials. Above all, polyallenes represented by polyparaphenylenes (PPPs), polypyrroles, and polythiophenes have received considerable attention because of their increased conductivity due to doping.
In addition, the polymer conductive material becomes conductive by generating carriers having positive and negative charges in the molecule by oxidation and reduction, and the product at that time has oxidation and reduction ability. Therefore, its usefulness as an active material for batteries has been attracting attention.

[0003] Porphyrin molecules are small intramolecular HOMs.
Since it has an O-LUMO gap and incorporates almost all metal elements into the central hole, it can be said that it is a specific molecule among many organic compounds. Reflecting this feature,
Porphyrin molecules constitute compounds that play important roles in biological systems. Further, it is used as a substance that absorbs external energy and converts it into other energy, and has a very wide functional characteristic. In addition, the porphyrin molecules have attracted attention as a block unit for assembling and constructing a π-conjugated structure because they have rigidity, high stability, strong electron absorption properties, a small energy gap, and a strong energy gap. It has many features, such as the ability to produce optical and redox properties through the emission of a variety of fluorescent light and appropriate metallization.

Recently, we have found a meso-meso coupling reaction of 5,15-diallyl-substituted Zn (II) -porphyrins by treatment with Ag (I) salts or electrochemical oxidation at the anode ( For the former, Osuka, A .; Shi
midzu, H. Angew.Chem., Int.Ed.Engl. 1997, 36, 135., for the latter, Ogawa, T .; Nishimoto, Y .; Yoshida, N .; Ono,
N .; Osuka, AJ Chem. Soc., Chem. Commun. 1998, 337.). In porphyrin, the meso position is
Positions 5, 10, 15 and 20. By the way, al
The pha position is 1,4,6,9,11,14,16,1
9 positions and beta positions are 2,3,7,8,12,1
Positions 3, 17, and 18 (see FIG. 7). Interestingly, the regioselectivity of the meso-meso coupling is extremely high, and the latter method (electrochemical oxidation) allows linear and porphyrin-constituting carbon to directly bind porphyrin sequences up to 8 solids (octamer). ) Can be formed. However, the porphyrin sequence could not be further increased by the proposed method.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for obtaining a meso-meso-coupled compound having a porphyrin sequence of more than 8 and a 5,15-diallyl-substituted Zn (II) -porphyrin. And a compound having a porphyrin sequence of more than 8. The present inventor has proposed a meso-meso described in the above-mentioned document to solve the above-mentioned problem.
Based on the coupling reaction, in order to find conditions for accelerating (promoting) the reaction, various attempts were made on compounds to be coexisted in the reaction system and other reaction conditions. Among them, the present inventors have proposed N, N-dimethylacetamide (N, N-dime
With the addition of thylacetamide (DMA) and / or slight heating, AgPF ₆ and Ag
(I) -Promoted meso-meso coupling reaction is a long-chain poly (porphyrinylene) having a porphyrin sequence of more than 8
Is found to be extended until it is generated. Above and D
Similar to MA, the effect of accelerating the polymerization is that DMF (N, N-
Dimethylformamide), HMPA (hexamethylphosphoamide) and DMSO (dimethylsulfoxide), and the effect of the acceleration is DMA>
It was also found that DMF-HMPA> DMSO.

[0006]

Means for Solving the Problems A first aspect of the present invention is that of the general formula 1

[0007]

Embedded image

A poly (5,15-diaryl-substituted Zn (II) -porphyrinylene) compound represented by the general formula (1)
Where n is an integer of 9 or more. R in the aryl substituent is
R is a bulky alkyl group or a higher alkoxy group which enhances solubility in a solvent, and R may be the same or different. ), The metal-free porphyrylene compound and Zn are represented by Mg, Ca, Sr, Ba, S
c, Y, La, Ce, Pr, Nd, Sm, Eu, Gd,
Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Z
r, Hf, V, Nb, Ta, Th, U, Cr, Mo,
W, Mn, Tc, Re, Fe, Ru, Os, Co, R
h, Ir, Ni, Pd, Pt, Cu, Ab, Au, C
d, Hg, Al, Ga, In, Tl, Si, Ge, S
The porphyrinylene compound substituted with n, Pb, As, Sb, and Bi. Preferably, all R in the aryl substituent is a tert-butyl group or an alkoxy group having 8 or more carbon atoms, wherein the poly (5,15-diaryl-substituted Zn (II) -porphyrinylene) is used. Compounds. A second aspect of the present invention is to use the general formula

[0009]

Embedded image

(In the formula, R is the same as in the general formula 1.)
A 5,15-diaryl-substituted Zn (II) -porphyrin compound represented by the following formula, in a solvent in which a silver salt that promotes regioselective meso-meso coupling is present, contains at least DMA, DMF, HMPA and DMSO in the solvent. Adding a small amount of one, and / or heating the solvent to obtain
Is a method for producing a poly (5,15-diaryl-substituted Zn (II) -porphyrinylene) compound of the formula (1). Preferably, the solvent is a halogenated solvent, for example CHCl ₃ (chloroform), wherein the poly (5,15-
This is a method for producing a diaryl-substituted Zn (II) -porphyrinylene) compound.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail. A. The poly (5,15-diaryl-substituted Zn (I
The reaction for producing the I) -porphyrinylene) compound can be represented by the following reaction formula 1.

[0012]

Embedded image

(In the reaction formula 1, n and R are the same as defined in the general formula 1.) The reaction was carried out in CHCl ₃ at 20 ° C. under the reaction conditions without DMA and without heating. , R is a tert-butyl group, and 5,15-diaryl-substituted Zn (II) -porphyrin (1a) (raw material) is mixed with 1.5 equivalents of AgPF6 and 4
After reacting for 1 hour, 1a (40-50%) (raw material), 2a (dimer: 25-30%), 3a (trimer:
5-7%) and 4a (tetramer: 1-2%) and only small amounts of larger oligomers were obtained [FIG. 1 (a)] (corresponding to the prior art). I do.) To promote regioselective meso-meso coupling instead of AgPF ₆ in Reaction Scheme 1, Ag
A monovalent silver salt having a non-nucleophilic anion such as ClO ₄ and AgBF ₄ can be used. The fact that the metal incorporated in the raw material monomer is Zn also indicates that the regioselective meso
-Contributes to the meso coupling reaction.

B. About the reaction solvent. The reaction solvent is selected from halogenated solvents, for example, lower halogenated alkylenes such as chloroform (CHCl ₃ ) and methylene chloride, halogenated benzenes such as chlorobenzene and the like, and polymerized poly (5,15-diaryl-substituted Zn ( Those which dissolve the (II) -porphyrinylene) compound are preferred. C. About the effect of the compound coexisting in the solvent. In contrast to the above reaction, it was found that the presence of only a small amount of DMA (0.5% based on CHCl ₃ ) could significantly improve the oligomer formation reaction within 0.5 hours. [(B) of FIG. 1]. Further, the mixture obtained by this reaction was converted to MALDI-TOF (Ma
trix-assited Laser Desorption Ionization-Time of F
FIG. 2 (a) shows the results of measurement by mass spectrometry (MS) using light (light). From this measurement result, 2
The presence of various porphyrin oligomers up to dimer (porphyrin sequence up to 22) and higher multimers was confirmed. From around 700 (corresponding to the mass of the porphyrin with zinc removed) to 16500 Da (corresponding to the monomer to 22 mer), a molecular ion peak increasing by the molecular weight corresponding to one porphyrin ring is observed. FIG. 2B shows the results obtained by measuring the fraction eluted by GPC-HPLC by the UV-absorption method. Since the solubility is low when the zinc form is used, the UV-vis absorption spectrum of the fraction eluted in order of molecular weight was measured by GPC-HPLC as a free base. GPC
-The spectrum of Fig. 2 (b) obtained for the HPLC fraction shows the broadening of the wavelength range in the exciton fission Soret bands (Soret bands: 400 nm) and the Q-ban.
indicates a gradual red shift in the nds (red area),
It was found that large porphyrins were formed by meso-meso coupling with high regioselectivity. The porphyrin multimer mixture thus produced has already been synthesized and shows the same tendency as the absorption spectrum of meso-meso-bound porphyrins of less than or equal to the octamer having a known structure, so that porphyrin multimers bonded in the same manner are formed. Can be concluded. From the relationship between the molecular weight of each oligo (porphyrinylene) and the retention time of GPC-HPLC, the main oligomer eluted at about 19 minutes corresponds to the 8.9-mer, and eluted at about 14.5 minutes. The largest detectable oligomer that corresponds to about 50 mer.

The formation of the polymer depends on the amount of DMA,
It was found to be most effective when 0.5 to 3% of DMA was added. At less than 0.5%, the acceleration effect was negligible. At more than 3%, the acceleration showed a decrease with increasing DMA, and the addition of 20% of DMA completely suppressed the acceleration effect. Like DMA, DMF, HMP
A and DMSO also had the effect of promoting the polymerization, but the effect of acceleration was DMA> DMF to HMPA> D
The order was MSO.

D. On the effect of temperature on the reaction. The present inventors have discovered that the polymerization can be accelerated only by heating the reaction temperature to 45 ° C. 24
After a reaction of time, Mw = 1 with a polydispersity of 1.37.
Formation of a 3000 Da polymer (corresponding to about 17-18 mer) was confirmed. This was noteworthy. However, the effect of accelerating polymerization by heating the monomer 1a (5,15-diaryl-substituted Zn (II) -porphyrinylene in which R is a tert-butyl group) is as follows.
After that, although the chain length progresses slightly slowly,
It was found that after about 70% it had saturated at about 70%. The effect of accelerating the polymerization by the heating appears at a temperature of at least 30 ° C.

E. The effect of the combination of the compound coexisting in the solvent and the temperature on the reaction. The effect of accelerating the polymerization of these combinations is synergistic.

F. About the effect of a polymer from a monomer (5,15-diaryl-substituted Zn (II) -porphyrinylene) on the polymerization of a solvent-soluble polymer. The present inventor believes that the poor solubility of the long-chain porphyrin sequence (polymer) formed may have prevented the progress of the polymer, and in order to overcome this, the more soluble raw material 1b [R Was replaced with an octyloxy group (OC ₈ H ₁₇ )], and it was argued that 1 was probably due to the bulky 3,5-dioctyloxyphenyl substituent.
It was found that the reactivity was lower than a. At 20 ° C.
After reacting with 1.5 equivalents of AgPF _{6 in} CHCl ₃ for 24 hours, it was found that only 5% of 1b was consumed.

1. Effects of compounds coexisting in the reaction system. However, even in this monomer system (raw material 1b system), the addition of 0.5% of DMA causes the formation of poly (porphyrylene) having a polydispersity of 1.7 and a Mw = 45000 Da after 24 hours. It was found to improve. FIG. 5 shows the GPC-HPLC fraction, a (2
0-23 minutes), b (18 minutes), c (17 minutes), d (16 minutes)
Min), e (15 minutes), and f (14 minutes) and the absorption spectrum (dotted line), and the absorption spectra of 4,8 and 16-mer oligomers. The absorption wavelength has shifted to the longer wavelength side. The components to coexist in the reaction system are DMF,
The effect of replacing with HMPA and DMSO was slightly inferior to that of monomer 1a in terms of the degree of polymerization and the reaction time, but qualitatively unchanged. 2. The effect of heating the reaction system. As in the case of monomer 1a, heating to 45 ° C. produces a polymer with a polydispersity of 1.59 and Mw = 21500 Da, but requires a considerable induction period (10 hours) before the polymerization can be started Met. The effect of the heating is that the reaction at room temperature is smaller than in the case of the monomer 1a,
Largely observed.

3. The effect of the combination of compound and heating to coexist in the reaction system. Reaction of 1.5 equivalents of AgPF ₆ with monomer 1b
When carried out at 45 ° C. in the presence of 5% of DMA, the polymerization proceeds considerably and after 11 hours with a polydispersity of 1.60 and Mw = 750.
00Da poly (porphinirylene) is formed and 82
After a time, a poly (porfinirylene) having a Mw = 250,000 Da and a dispersity of 2.78 was formed. This point appears in FIG. 1C. These long-chain poly (porfinirylenes) have similar absorption [FIG. 1 (c)] and fluorescence spectra to oligo (porfinirylene) s of each size prepared from 1b, ie, 64-mer and 128-mer. FIG. 6 shows the relationship between the molecular weight of oligo (porphyrinylene) s (the number on the curve indicates the number of monomers) and the retention time of GPC-HPLC. Show. Therefore, if these reaction conditions are used, poly (porphinirylene) s of 200-mers or more can be easily produced from the soluble 1b monomer. From the liquid chromatography chart, 300
It has also been confirmed that ４００400-mers are formed.

From the above, although the mechanism of polymerization is not completely understood, poly (paraphenylene)
Similar to the reaction process proposed as the growth process of the oxidative chain length of (PPP), polymerization of Zn (II) porphyrin by one-electron oxidation by Ag (I) or the like and poly (5, It can be considered that the growth process of the chain length proceeds through the process of forming a poly (5,15-dihydroporphyrinylene) intermediate, which becomes 15-porphyrinylene).

As a coexisting compound, DMA exhibits an excellent accelerating effect as compared with DMF because DMA reduces a cation radical intermediate to a radical which is considered to be more active in growing the chain length. This suggests that the change is due to the role of DMA as a reducing agent.

In short, metalloporphyrins having no substituents around the meso-position and having no steric hindrance, such as 1a and 1b, can be used in the presence of 0.5 to 3% of DMA and / or under heating to obtain AgPF ₆ or It is understood that poly (5,15-diaryl-substituted Zn (II) -porphyrinylenes) can be formed by regioselective polymerization by reaction with Ag (I) salts. That is, 5,1 having an R group
The 5-position aryl substituent suggests that it has a significant effect on the regioselective polymerization reaction.

[0024]

As described above, poly (5,15-diaryl-substituted Zn (II) -porphyrinylene) s can be made higher in molecular weight by the progress of the polymerization reaction. It is said that absorption characteristics, light-emitting characteristics, semiconductor or conductive characteristics, and photoelectric characteristics are improved, and the multifunctionality of porphyrin can be further improved. Brings excellent effects. Further, it is clear that the improvement of the π-conjugated system leads to the improvement of the conductive properties, and the compounds of the present invention are expected to be used in new fields such as molecular wires.
Further, when the polymer represented by the general formula 1 of the present invention is treated with an acid such as concentrated hydrochloric acid, a free base porphyrin polymer from which zinc has been removed is obtained, and a method of incorporating metal ions into ordinary porphyrin is described. By applying, a porphyrin-polymer incorporating the following metals can be synthesized. That is, as metals that can be incorporated, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu,
Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, N
b, Ta, Th, U, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, C
o, Rh, Ir, Ni, Pd, Pt, Cu, Ab, Au, Cd, Hg, Al, Ga,
In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi and the like can be mentioned.

[Brief description of the drawings]

FIG. 1: 1.a for 1a or 1b in CHCl ₃ .
GPC-HPLC chart (413 nm) of the reaction product to which 5 equivalents of AgPF ₆ was added, (a) 0.5% using (b) 1a of the reaction mixture obtained under the reaction conditions without DMA and without heating % DMA and the reaction product at room temperature ((a) monomer to (q) 17-mer)) and (c) 0.5% using 1b.
% Absorption spectrum of the reaction product at 45 ° C. for 11 hours (dotted line: 64-mer) and for 82 hours (128-mer) in the presence of% DMA

FIG. 2: 1.5 equivalents of A to 1a in CHCl ₃
GPF ₆ was added, the reaction product at room temperature was added a 0.5% DMA, mass spectrum using (a) MALDI-TOF (MS ), and soluble in a solvent and the free base by (b) acid treatment Absorption spectra of fractions eluted in order of molecular weight by GPC-HPLC [(a) to (q)
Corresponds to FIG. 1 (b)]

FIG. 3 shows an absorption spectrum (a) and an emission spectrum (b) of a 128-mer using 1b.

FIG. 4 shows the relationship between the molecular weight of oligo (porphyrinylene) s obtained using 1a and the retention time of GPC-HPLC.

FIG. 5. GPC-HPLC fraction, a (20-23)
Min), b (18 minutes), c (17 minutes), d (16 minutes), e
(15 minutes), and the relationship between f (14 minutes) and the absorption spectrum (dotted line), and the absorption spectra of 4,8 and 16-mer oligomers.

FIG. 6 shows the relationship between the molecular weight of oligo (porphyrinylene) s obtained using 1b (the number on the curve indicates the number of the monomers) and the retention time of GPC-HPLC.

FIG. 7: Porphyrin numbering

Claims (4)

(57) [Claims] 1. A poly (5,15-diaryl-substituted Zn (II) -porphyrylene) compound represented by the general formula 1:
The metal-free porphyrinylene compound and Zn
With Mg, Ca, Sr, Ba, Sc, Y, La, Ce, P
r, Nd, Sm, Eu, Gd, Tb, Dy, Ho, E
r, 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, P
t, Cu, Ab, Au, Cd, Hg, Al, Ga, I
n, Tl, Si, Ge, Sn, Pb, As, Sb, Bi
The porphyrinylene compound substituted with Embedded image (In the general formula 1, n is an integer of 21 or more, R in the diaryl substituent is a bulky alkyl group or a higher alkoxy group that enhances the solubility in the reaction solvent, and Rs may be the same or different. Good.) 2. All the R's in the diaryl substituent are te
The poly (5,15) according to claim 1, which is an rt-butyl group or an alkoxy group having 8 or more carbon atoms.
-Diaryl-substituted Zn (II) -porphyrylene) compound, the metal-free porphyrylene compound and Zn by Mg, Ca, Sr, Ba, Sc, Y, La, C
e, Pr, Nd, Sm, Eu, Gd, Tb, Dy, H
o, 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, P
d, Pt, Cu, Ab, Au, Cd, Hg, Al, G
a, In, Tl, Si, Ge, Sn, Pb, As, S
b, the porphyrinylene compound substituted with Bi. 3. General formula 2 (In the general formula 2, R is a bulky alkyl group or a higher alkoxy group which enhances the solubility in a solvent. , May be different.) In a solvent in which a silver salt that promotes regioselective meso-meso coupling is present, and the solvent contains at least DM.
A method for producing a poly (5,15-diaryl-substituted Zn (II) -porphyrinylene) compound of the general formula 1 by adding a small amount of one of A, DMF, HMPA and DMSO, and / or heating the solvent. 4. The method for producing a poly (5,15-diaryl-substituted Zn (II) -porphyrinylene) compound according to claim 3, wherein the solvent is a halogenated solvent.