JP2004161754A - Hexadeca-azanaphthalocyanine compound and its polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new hexadeca-azanaphthalocyanine compound useful as an optical recording material, an electron transport layer material for EL, a battery material, an oxidation-reduction catalyst, an agrochemical intermediate and the like and polymers of the same. <P>SOLUTION: The hexadeca-azanaphthalocyanine compound is expressed by formula [I] (wherein M expresses hydrogen (2H), a metal, a metal oxide, a metal hydroxide, an acyl metal, an alkoxy metal, a siloxy metal or a metal halide). The polymers are a one-dimensional polymer prepared by bonding the hexadeca-azaphthalocyanine compound expressed by formula [I] to arrange M on one axis through atomic groups and a two-dimensional polymer prepared by mutually bonding terminal cyano groups. <P>COPYRIGHT: (C)2004,JPO

Description

  The present invention relates to a novel hexadecazanaphthalocyanine compound useful as an optical recording material, an electron transport layer material for EL, a battery material, an agricultural and pharmaceutical intermediate, and the like.

Conventionally, as an optical recording material, satisfying conditions such as high solubility in an organic solvent, absorption at a specific wavelength, etc., and having resistance to light and oxygen to withstand practical use, It is required to have a high threshold value, a low thermal conductivity, etc., and in a laser printer, have an appropriate ionization potential to obtain a high charge injection effect in combination with a charge transport material, and a high sensitivity latent image. It is necessary to satisfy conditions such as low dark decay, resistance to laser light and oxygen, etc. A naphthalocyanine compound derivative is known as a material such as an optical recording material, an electron transport layer material for EL, and a battery material satisfying such conditions (for example, see Patent Document 1).
JP-A-3-232886

  An object of the present invention is to provide a novel compound that can be a more useful material than conventionally known materials such as an optical recording material, an electron transport layer material for EL, a battery material, a redox catalyst, an agrochemical intermediate, and the like. It is in.

  The present inventors have found that a compound having a cyano group at a terminal in a specific naphthalocyanine compound derivative is extremely useful as an optical recording material, an electron transport layer material for EL, a battery material, a redox catalyst, an agricultural and pharmaceutical intermediate, and the like. Further, in these specific naphthalocyanine compound derivatives, a one-dimensional polymer in which a compound having a terminal cyano group is bonded via an atomic group so that M is arranged uniaxially, or a terminal cyano group is bonded to each other. The two-dimensional polymer formed by this method has high electron-accepting properties and is useful as an optical recording material, an electron transport layer material for EL, a battery material, a redox catalyst, an agro-pharmaceutical intermediate, and the like. It was completed.

  That is, the present invention provides a compound of the formula [I]

［式中、Ｍは水素（２Ｈ）、金属、金属酸化物、金属水酸化物、アシル金属、アルコキシ金属、シロキシ金属又は金属ハロゲン化物を示す。］で表されるヘキサデカアザナフタロシアニン化合物に関する。

[Wherein, M represents hydrogen (2H), metal, metal oxide, metal hydroxide, acyl metal, alkoxy metal, siloxy metal, or metal halide. And a hexadecazanaphthalocyanine compound represented by the formula:

  Also, the present invention provides a compound of the formula [I]

［式中、Ｍは、金属、金属酸化物、金属水酸金属、アシル金属、アルコキシ金属、シロキシ金属又は金属ハロゲン化物を示す。］で表されるヘキサデカアザナフタロシアニン化合物が、原子団を介してＭが一軸上に配置するように結合した式［II］

[In the formula, M represents a metal, metal oxide, metal hydroxide metal, acyl metal, alkoxy metal, siloxy metal, or metal halide. [II] in which a hexadecaazanaphthalocyanine compound represented by the formula [II] is bonded via an atomic group so that M is arranged uniaxially.

［式中、Ｍは式［Ｉ］におけるＭと同じものを示し、Ｌは原子団を示す。］で表されるヘキサデカアザナフタロシアニン化合物の一次元重合体（請求項２）に関し、好ましくは、原子団Ｌが、ｐ−ジイソシアノベンゼンであることを特徴とする請求項２記載のヘキサデカアザナフタロシアニン化合物の一次元重合体（請求項３）や、オリゴマーであることを特徴とする請求項２又は３記載のヘキサデカアザナフタロシアニン化合物の一次元重合体（請求項４）に関する。

[Wherein, M represents the same as M in formula [I], and L represents an atomic group. The one-dimensional polymer of hexadecaazanaphthalocyanine compound represented by the formula (Claim 2), wherein preferably, the atomic group L is p-diisocyanobenzene. The present invention relates to a one-dimensional polymer of an azanaphthalocyanine compound (claim 3) or a one-dimensional polymer of a hexadecaazanaphthalocyanine compound according to claim 2 or 3, which is an oligomer.

  Further, the present invention provides a compound of the formula [I]

［式中、Ｍは水素（２Ｈ）、金属、金属酸化物、金属水酸化物、アシル金属、アルコキシ金属、シロキシ金属又は金属ハロゲン化物を示す。］で表されるヘキサデカアザナフタロシアニン化合物の末端のシアノ基が相互に結合した式［III］

[Wherein, M represents hydrogen (2H), metal, metal oxide, metal hydroxide, acyl metal, alkoxy metal, siloxy metal, or metal halide. [III] in which terminal cyano groups of a hexadecazanaphthalocyanine compound represented by the formula

［式中、Ｍは式［Ｉ］におけるＭと同じものを示す。］で表されるヘキサデカアザナフタロシアニン化合物の二次元重合体（請求項５）に関し、好ましくは、オリゴマーであることを特徴とする請求項５記載のヘキサデカアザナフタロシアニン化合物の二次元重合体（請求項６）に関する。

[Wherein, M represents the same as M in the formula [I]. The two-dimensional polymer of a hexadecaazanaphthalocyanine compound represented by the formula (Claim 5), which is preferably an oligomer. Regarding item 6).

  The hexadecazana phthalocyanine compound of the present invention and the polymer thereof have solvent solubility, have a maximum absorption in near ultraviolet rays, and have n-type OPC (organic photoconductor) materials, electrophotographic photoreceptors, and optical recording materials. It is useful as an electron transport layer material for EL, a freshness maintaining agent, a redox catalyst, a battery material, an agricultural and pharmaceutical intermediate, and the like.

The hexadecazanaphthalocyanine compound of the present invention is a hexadecazanaphthalocyanine compound represented by the formula [I] (abbreviated as MHWANcOC). In the formula [I], M represents hydrogen (2H), a metal or a metal oxide. A metal, a metal hydroxide, an acyl metal, an alkoxy metal, a siloxy metal or a metal halide, and such M is specifically -H and H-, Mg, AlCl, SiCl ₂ , Si (OH) ₂ , Si (COCH ₃ ) ₂ , Si (OCH ₃ ) ₂ , Si (OSi (CH ₃ ) ₃ ) ₂ , Ca, TiO, VO, Cr, Mn, Ru, Co, Ni, Cu, Zn, Ga, Ge, Examples include ZrO, Nb, Mo, Fe, Pd, InCl, InBr, Sn, SnCl ₂ , SnBr ₂ , SnI ₂ , Ta, Pb, Bi, and lanthanides.

  The hexadecazanaphthalocyanine compound represented by the formula [I] is represented by the formula [IV]

で表される２，３，６，７−テトラシアノ−１，４，５，８−テトラアザナフタレン（ＴＣＮＡと略記する。）と金属、金属酸化物、金属水酸化物、アシル金属、金属錯塩、シロキシ金属、金属ハロゲン化物等あるいは何も用いず（Ｍ：水素（２Ｈ））に、トリクロルベンゼン、ジクロルベンゼン、クロルナフタレン、スルフォラン等の高沸点不活性溶媒中で数時間から数１０時間、１００〜２５０℃に加熱することにより製造される。アシル金属、金属錯塩としては、好ましくは金属アセテート、金属ホルメート、金属アセチルアセテート等である。

2,3,6,7-tetracyano-1,4,5,8-tetraazanaphthalene (abbreviated as TCNA) and a metal, metal oxide, metal hydroxide, acyl metal, metal complex, Siloxy metal, metal halide or the like or nothing (M: hydrogen (2H)) in a high boiling point inert solvent such as trichlorobenzene, dichlorobenzene, chloronaphthalene or sulfolane for several hours to several tens of hours. Manufactured by heating to ~ 250 ° C. The acyl metal and metal complex salt are preferably metal acetate, metal formate, metal acetyl acetate and the like.

The one-dimensional polymer of the hexadecaazanaphthalocyanine compound of the present invention has a formula wherein a hexadecaazanaphthalocyanine compound of the present invention represented by the formula [I] is bonded via an atomic group such that M is arranged on one axis. It is a one-dimensional polymer of a hexadecazanaphthalocyanine compound represented by [II], and in the formula [I], M is a metal, metal oxide, metal hydroxide metal, acyl metal, alkoxy metal, siloxy metal or metal halogen. In the formula [II], M is the same as M in the formula [I]. As such M, specifically, Mg, AlCl, SiCl ₂ , Si (OH) ₂ , Si (COCH ₃ ) ₂ , Si (OCH ₃ ) ₂ , Si (OSi (CH ₃ ) ₃ ) ₂ , Ca, TiO, VO, Cr, Mn, Ru, Co, Ni, Cu, Zn, Ga, Ge, ZrO, Nb, Mo, Fe, Pd, InCl, InBr, Sn, SnCl 2, SnBr 2, SnI 2, Ta, Pb , Bi, lanthanides and the like. Examples of the atomic group L that bonds M of the hexadecazanaphthalocyanine compound to each other include p-diisocyanobenzene. As the one-dimensional polymer of the hexadecazanaphthalocyanine compound of the present invention, for example, oligomers having M of cobalt and iron and a degree of polymerization of 6 to 9 are slightly dissolved in a solvent such as dimethylformamide (DMF) at 90 ° C. Polymers that dissolve and have a degree of polymerization greater than 10 are insoluble in solvents such as dimethylformamide (DMF) at 90 ° C. Such a one-dimensional polymer has a large number of cyano groups, has a high electron-accepting property, and is useful as a material for EL batteries and the like.

  As a method for producing a one-dimensional polymer of a hexadecazanaphthalocyanine compound of the present invention, a hexadecazanaphthalocyanine compound represented by the formula [I] and a compound which becomes an atomic group mutually bonded to these compounds, for example, p- A method in which diisocyanobenzene is heated to 100 to 250 ° C. for several hours to several tens of hours in a high boiling point inert solvent such as dichlorobenzene, trichlorobenzene, and chloronaphthalene can be used.

  The two-dimensional polymer of the hexadecaazana phthalocyanine compound of the present invention is a hexadecazana phthalocyanine compound represented by the formula [III] in which terminal cyano groups of the hexadecaazana phthalocyanine compound represented by the above formula [I] are mutually bonded. It is a two-dimensional polymer of a phthalocyanine compound. In the formula [III], M has the same meaning as that represented by M in the above formula [I]. Specific examples of the two-dimensional polymer of the hexadecaazanaphthalocyanine compound of the present invention include the following formula [IIIa] having a degree of polymerization of 4 of the hexadecazanaphthalocyanine compound represented by the formula [I].

に示すオリゴマーや、式［Ｉ］で表されるヘキサデカアザナフタロアニン化合物の重合度７の下記式［IIIｂ］

Or a hexadecaazanaphthaloanine compound represented by the following formula [IIIb] having a degree of polymerization of 7:

に示すオリゴマー等である。

And the like.

  In the two-dimensional polymer of the hexadecaazanaphthalocyanine compound of the present invention represented by the formula [IIIa] or [IIIb], when M is copper or nickel, hexamethylphosphoric triamide (HMPT) at 150 ° C. And a polymer having a higher degree of polymerization is insoluble in a solvent such as hexamethylphosphoric triamide (HMPT) at 150 ° C. Further, such a two-dimensional polymer has a high electron-accepting property and is useful as a material for an EL battery or the like.

As a method for producing a two-dimensional polymer of a hexadecazanaphthalocyanine compound of the present invention, a hexadecazanaphthalocyanine compound is dissolved in a solvent such as acetone, tetrahydrofuran (THF), N, N-dimethylformamide (DMF), and the solution is dissolved. The liquid may be applied to the inner wall of the reaction tube to form a thin film, for example, heated at 250 to 500 ° C. for several hours to several tens of hours under reduced pressure of 1 mmHg or less.
The compound of the present invention was determined by MASS spectrum, IR, elemental analysis and the like.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the technical scope of the present invention is not limited to these examples.

Preparation of M = Co form (CoHDANcOC)

  In a 100 ml four-necked flask equipped with a reflux condenser with a drying tube, a thermometer, an argon gas inlet tube, and a mechanical stirrer, 10 ml of sulfolane subjected to precision distillation, 500 mg (2.2 mmol) of TCNA and 100 mg (0. (56 mmol) of cobalt acetate anhydrate was added thereto and reacted at 160 ° C. for 24 hours while stirring. After cooling, the reaction solution was added dropwise while stirring with 200 ml of chloroform to precipitate the target component. The precipitate was collected by filtration and washed with chloroform to obtain 292 mg of a black powder with a metallic luster (55% yield). From the following analysis results, it was found that the target was CoHDANcOC. It was soluble in polar solvents such as acetone, tetrahydrofuran (THF) and N, N-dimethylformamide (DMF) and exhibited a purple color.

Elemental analysis (calculated): C 48.75% (48.64%), N 45.27% (45.39%)
TOF-Mass spectrum parent peaks (Z / e) = 988 and 989 (calculated molecular weight = 987.65), maximum wavelength of visible absorption spectrum in DMF = 552 nm, 737 nm (in DMF).

Preparation of M = hydrogen (2H) form (H ₂ HDANcOC)

In a 100 ml four-necked flask equipped with a reflux condenser equipped with a drying tube, a thermometer, an argon gas inlet tube, and a mechanical stirrer, 10 ml of finely distilled sulfolane and 500 mg (2.2 mmol) of TCNA were placed, and the mixture was heated at 160 ° C. The reaction was carried out for 48 hours while stirring. After cooling, the reaction solution was added dropwise while stirring with 200 ml of chloroform to precipitate the target component. The precipitate was collected by filtration and washed with chloroform to obtain 120 mg of a black powder having a metallic luster (yield: 23%). From the analysis results shown below, it was found that the target was H ₂ HDANcOC.

  Elemental analysis (calculated): C 51.73% (51.62%), N 48.22% (48.17%), TOF-Mass spectral parent peak (Z / e) = 931 and 932 (calculated molecular weight = 930.74), visible in DMF Absorption spectrum maximum wavelength = 545,575,618,702, nm (in DMF).

  The cyclic voltammogram (hereinafter referred to as CV) of CoHDANcOC obtained in Example 1 was measured under the conditions shown in Table 1.

  The results are shown in Figure 1. The scale in FIG. 1 is a value for the Ag / AgCl reference electrode. From the results, it was found that CoHDANcOC was useful as a battery material.

The oxidation / reduction potential of CoHDANcOC obtained in Example 1 was measured. Table 2 shows the results.
In _{20 ℃ E VS.NHE = E VS. Ag} / AgCl + 226mV

  From the results, it was found that CoHDANcOC was useful as a redox reaction catalyst.

Preparation of CoHDANcOC one-dimensional polymer In a 100 ml four-necked flask equipped with a reflux tube equipped with a calcium chloride drying tube, a thermometer, an argon gas inlet tube, and a mechanical stirrer, 5 ml of precision distilled dichlorobenzene, 100 mg (0.10 mmol) of CoHDANcOC and 130 mg (1.0 mmol) of p-diisocyanobenzene (dib) were added and reacted at 115 ° C. for 48 hours. After cooling, the reaction solution was filtered, and the residue was washed with chloroform, acetone, and cold dimethylformamide (DMF) to obtain 90 mg (yield: 80%) of the target compound in black. The target substance is generally insoluble or infusible, but slightly dissolved (less than 0.5% of the entire target substance) in hot DMF at 90 ° C. The soluble part was subjected to TOF-Mass spectrum analysis, and oligomers were identified from the following peaks corresponding to the calculated values of n = 6 to 9. The insoluble matter was found to be a target substance having n ≧ 10 as a main component.

M / Z = 6824,6825 (n = 6: calculated molecular weight = 6822.377)
= 7940,7941 (n = 7: calculated molecular weight = 7938.085)
= 9055,9056 (n = 8: calculated molecular weight = 9053.793)
= 10171,10172 (n = 9: calculated molecular weight = 10169.500)

The maximum absorption wavelength of the ultraviolet-visible spectrum in hot DMF was 552 nm for CoHDANcOC of the monomer, while the soluble portion of the target substance was shifted to 546 nm, confirming the presence of a one-dimensional polymer. The infrared absorption spectrum, isocyanide stretching vibration 2117cm ^-1 was observed in addition to the cyano group stretching vibration 2233cm ^-1, the desired product structure is supported.

Elemental analysis: C51.82%, H0.379%, N42.55%; C / N1.218
Calculated value as a 10-mer ([CoHDANcOC (dib)] ₁₀ ): C51.937%, H0.393%,
N42.448%, Co5.222%, C / N1.224
Calculated value as n-mer ([CoHDANcOC (dib)] _n n → ∞): C 51.672%, H0.361%,
N42.684%, Co5.282%, C / N 1.211

Preparation of FeHDANcOC one-dimensional polymer The reaction was carried out in the same manner as in Example 5 except that 100 mg (0.10 mmol) of FeHDANcOC was used, to obtain 79 mg (yield 70%) of a black target product. The target substance is generally insoluble / infusible, but slightly dissolved (less than 0.5% of the entire target substance) in hot DMF at 90 ° C. The soluble part was subjected to TOF-Mass spectrum analysis, and oligomers were identified from the following peaks corresponding to the calculated values of n = 6 to 9. The insoluble matter was found to be a target having n ≧ 10 as a main component.

M / Z = 6805,6806 (n = 6: calculated molecular weight = 6803.848)
= 7918, 7919 (n = 7: calculated molecular weight = 7916.467)
= 9031, 9032 (n = 8: calculated molecular weight = 9029.087)
= 10143, 10144 (n = 9: calculated molecular weight = 10141.707)

Further, the maximum absorption wavelength of the ultraviolet-visible spectrum in hot DMF was 552 nm for the monomer FeHDANcOC, while the soluble portion of the target substance was shifted to 546 nm, confirming the presence of the one-dimensional polymer. The infrared absorption spectrum, 2117 ^{cm -1} isocyanide stretching vibration in addition to the cyano group stretching vibration 2233cm ^-1 was observed, the desired product structure is supported.

Elemental analysis: C 51.94%, H 0.384%, N42.77%, C / N 1.214
Calculated value as a 10-mer ([FeHDANcOC (dib)] ₁₀ ): C52.080%, H0.394%,
N42.564%, Fe 4.962%, C / N1.224
Calculated value as n-mer ([FeHDANcOC (dib)] _n n → ∞): C51.816%, H0.362%,
N2.803%, Fe42.803%, C / N 1.211

Evaluation of Lithium Secondary Battery Using CoHDZNcOC One-Dimensional Polymer A 2016 coin-type battery was used for battery evaluation, and a conductive material was used for the positive electrode to be 50 wt / wt% of CoHDANcOC (dib) one-dimensional polymer obtained in Example 5. A thin film having a thickness of 100 μm was prepared by adding 30 wt / wt% of acetylene black as an auxiliary agent and binding with 20 wt / wt% of polyvinylidene fluoride. The negative electrode was made of a metallic lithium foil having a thickness of 130 μm, and a 0.2 M LiPF ₆ / dimethoxyethane solution was used as an electrolytic solution, soaked into a polypropylene nonwoven fabric separator having a porosity of 40% and a thickness of 25 μm. Charging is performed in a constant current charging mode with an upper limit voltage of 4.5 V, and discharging is performed by (1) constant capacity termination constant current discharging of a capacity corresponding to 3 to 5 electrons of the polymer, and (2) 1.0 V. The test was performed in two ways: constant potential termination and constant current discharge at the lower limit voltage (cutoff voltage). Table 3 shows the results.

  From the results, it was found that the CoHDANcOC (dib) one-dimensional polymer has a high energy density, a high output voltage, a long cycle life, and is useful as a battery material.

Evaluation of lithium secondary battery using one-dimensional FeHDANcOC polymer Except for using 50 wt / wt% of FeHDANcOC (dib) polymer obtained in Example 6 in place of CoHDANcOC (dib) polymer for the positive electrode component, A charge / discharge test was conducted in the same manner as in No. 7. Table 4 shows the results.

  From the results, it was found that the FeHDANcOC (dib) one-dimensional polymer has a high energy density, a high output voltage, a long cycle life, and is useful as a battery material.

Preparation of CuHDANcOC two-dimensional polymer (300 ° C)
200 mg (0.20 mmol) of CuHDANcOC was dissolved in acetone subjected to precision distillation, and applied to the inner wall of a heat-resistant glass reaction tube to form a thin film. The reaction tube was heated to 300 ° C. under a reduced pressure of 1 mmHg or less, and reacted for 12 hours. After cooling, the mixture was washed with acetone and DMF to obtain 150 mg (yield: 75%) of the target black powder. The target substance was generally insoluble / insoluble, but slightly dissolved in hexamethylphosphoric triamide (HMPT) at 150 ° C. The soluble portion was subjected to TOF-Mass spectrum analysis, and oligomers were confirmed from the following peaks corresponding to the calculated values of n = 4 and n = 7.

M / Z = 3970,3971 (n = 4: calculated molecular weight = 3968.759)
= 6947,6948 (n = 7: calculated molecular weight = 6945.328)
Elemental analysis: C 48.37%, H 0.0%, N 45.11%, C / N 1.072
Calculated values: C 48.421%, H 0.0%, N 45.174%, Cu 6.405%, C / N 1.072

In addition, the maximum absorption wavelength of the ultraviolet-visible spectrum in HMPT was such that the target soluble portion was shifted to a long wavelength of 587 nm, while the CuHDANcOC of the monomer was 574 nm, and thus the presence of the two-dimensional oligomer was confirmed. In the infrared absorption spectrum, most of the cyano group at 2230 cm ⁻¹ remained, and it was found that the acceptor property was not impaired even when the oligomer was obtained.

Preparation of CuHDANcOC two-dimensional polymer (350 ° C, 400 ° C)
The reaction was carried out in the same manner as in Example 9 except that the heating temperature was changed to 350 ° C. and 400 ° C. instead of 300 ° C., and 180 mg (yield 90%) (350 ° C.) and 190 mg (yield 95 %) (400 ° C.). The target product was insoluble and infusible, there was no portion extracted by HMPT at 150 ° C., and the infrared absorption spectrum showed a spectrum without an unclear characteristic characteristic of a two-dimensional polymer.

Elemental analysis (350 ° C): C 48.33, H 0.0, N 45.12%, C / N 1.071
Elemental analysis (400 ° C): C 48.30, H 0.0, N 45.22%, C / N 1.068
Calculated value: C 48.421, H 0.0, N 45.174, Cu 6.405%, C / N 1.072

  It has been found that the two-dimensional polymerization proceeds more rapidly as the reaction temperature increases to 350 ° C. and 400 ° C.

Preparation of NiHDANcOC two-dimensional polymer (300 ° C)
Except that 200 mg of NiCuHDANcOC was used, 160 mg (yield: 80%) of the target black powder was obtained in the same manner as in Example 9. The target substance was generally insoluble / infusible, but slightly dissolved in 150 ° C. HMPT. The soluble portion was subjected to TOF-Mass spectrum analysis, and oligomers were confirmed from the following peaks corresponding to the calculated values of n = 4 and n = 7.

M / Z = 3951,3952 (n = 4: calculated molecular weight = 3949.348,)
= 6913,6914 (n = 7: calculated molecular weight = 6911.359)
Elemental analysis: C 48.72, H 0.0, N 45.44%, C / N 1.072
Calculated values: C48.659%, H0.0%, N 45.396, Ni 5.945%, C / N 1.072

The maximum absorption wavelength of the ultraviolet-visible spectrum in HMPT was 572 nm for NiHDANcOC of the monomer, while the soluble portion of the target product was shifted to 588 nm by long wavelength, confirming the presence of the two-dimensional oligomer. In the infrared absorption spectrum, most of the cyano group at 2230 cm ⁻¹ remained, and it was found that the acceptor property was not impaired even when the oligomer was obtained.

Evaluation of lithium secondary battery using CuHDZNcOC two-dimensional polymer A battery was prepared in the same manner as in Example 7, except that the CuHDZNcOC oligomer obtained in Examples 9 and 10 was used as a positive electrode component. Charging is performed in a constant current charging mode with an upper limit voltage of 4.6 V. Discharging is (1) constant capacity termination constant current discharging of a capacity corresponding to 3 to 5 electrons of the polymer, and (2) 1.0 V as a lower limit. The voltage (cutoff voltage) was used as a constant potential termination constant current discharge. Table 5 shows the results.

  From the results, under the discharge conditions of (2), a difference depending on the oligomer formation temperature was clearly recognized, and the oligomer having the largest remaining cyano group (= acceptor property) prepared at 300 ° C. gave a good result.

Evaluation of lithium secondary battery using NiHDANcOC two-dimensional polymer Charge and discharge in the same manner as in Example 12 except that 50 wt / wt% of NiHDANcOC polymer obtained in Example 11 was used instead of CuHDANcOC polymer for the positive electrode component The test was performed. Table 6 shows the results.

  From the results, it was found that the NiHDANcOC two-dimensional polymer has high battery capacity, energy density, and output voltage, has a long cycle life, and is useful as a battery material.

It is a figure showing CV measured in the example.

Claims (6)

Formula [I]

[Wherein, M represents hydrogen (2H), metal, metal oxide, metal hydroxide, acyl metal, alkoxy metal, siloxy metal, or metal halide. ] The hexadecaazana phthalocyanine compound represented by these. Formula [I]

[In the formula, M represents a metal, a metal oxide, a metal hydroxide metal, an acyl metal, an alkoxy metal, a siloxy metal, or a metal halide. [II] in which a hexadecaazanaphthalocyanine compound represented by the formula [II] is bonded via an atomic group so that M is arranged uniaxially.

[Wherein, M represents the same as M in the formula [I], and L represents an atomic group. The one-dimensional polymer of a hexadecaazana phthalocyanine compound represented by the following formula: The one-dimensional polymer of a hexadecazanaphthalocyanine compound according to claim 2, wherein the atomic group L is p-diisocyanobenzene. The one-dimensional polymer of the hexadecaazanaphthalocyanine compound according to claim 2, which is an oligomer. Formula [I]

[Wherein, M represents hydrogen (2H), metal, metal oxide, metal hydroxide, acyl metal, alkoxy metal, siloxy metal, or metal halide. [III] in which terminal cyano groups of a hexadecazanaphthalocyanine compound represented by the formula

[Wherein, M represents the same as M in the formula [I]. And a two-dimensional polymer of a hexadecazana phthalocyanine compound represented by the formula: The two-dimensional polymer of the hexadecaazanaphthalocyanine compound according to claim 5, which is an oligomer.

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