JP2006283014A - Linear tetrapyrrole dye - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a linear tetrapyrrole dye which has high compatibility with an organic substance and high solubility in an organic solvent, and exhibits good orientation in the case of the adsorption to an interface. <P>SOLUTION: The linear tetrapyrrole dye is synthesized by the oxidation and cleavage of a tetraphenyl porphyrin compound having an alkyl group and an alkoxy group on its phenyl group. Specifically, the compound is represented by formula (1), wherein R<SB>1</SB>, R<SB>2</SB>and R<SB>3</SB>each represents H, C<SB>n</SB>H<SB>2n+1</SB>or OC<SB>n</SB>H<SB>2n+1</SB>(excludes the case that all the R<SB>1</SB>, R<SB>2</SB>and R<SB>3</SB>are H), and n represents an integer of 3 to 30. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a linear tetrapyrrole dye, and particularly to a linear tetrapyrrole dye that can be used as a functional dye or the like.

  Functional dyes that change their structure according to the surrounding environment are considered to be widely applied to new sensors, analytical reagents, etc. Among them, they are highly sensitive to metal ions and organic solvents, and change the light absorption wavelength. Development of functional pigments is expected.

  As one of such functional dyes, linear tetrapyrrole dyes synthesized by oxidizing and cleaving a tetraphenylporphyrin ring, for example, villindione and biradienone compounds have been studied. Further, such a linear tetrapyrrole dye has a π-electron conjugated structure and has a flexible conformation, and is therefore known to have excellent responsiveness to external stimuli (Non-Patent Document 1). See).

However, the linear tetrapyrrole dye has not very good compatibility with organic substances, and has poor solubility in organic solvents. Also, the orientation when adsorbed on the interface was not very good. For this reason, the tetrapyrrole dyes are not suitable for use as functional dyes, adsorbents of physiologically active molecules such as sugars, and sensors for these physiologically active molecules.
Yamauchi et al., “A facile and versatile preparation of bilindiones and biladienones from tetraarylporphyrin”, (UK), Chemical Communications (Chem. Commun.) The Royal Society of Chemistry, March 2005, No. 10, pp. 1309-1311

  Accordingly, an object of the present invention is to provide a linear tetrapyrrole dye having high compatibility with an organic substance and high solubility in an organic solvent and good orientation when adsorbed on an interface.

  The main feature of the linear tetrapyrrole dye according to the present invention is that it is synthesized by oxidizing and cleaving a tetraphenylporphyrin compound having an alkyl group / alkoxy group in the phenyl group.

  The linear tetrapyrrole pigment of the present invention has high compatibility with organic substances and high solubility in organic solvents. Therefore, it has good orientation when adsorbed on the interface, and can be used as an adsorbent or sensor for physiologically active molecules such as functional dyes and sugars.

  The compound according to the present invention is a compound represented by the following general formulas (1), (3), (5), (7), (9), (11) and (14). Yes, specifically exemplified by the chemical formulas of Formula (2), Formula (4), Formula (6), Formula (8), Formula (10), (12), (13), and (15), respectively. It is the compound shown.

（式中、Ｒ₁，Ｒ₂，Ｒ₃はＨ，Ｃ_nＨ_2n+1又はＯＣ_nＨ_2n+1の何れか（ただし、Ｒ₁，Ｒ₂，Ｒ₃のすべてがＨの場合を除く。）を表し、ｎは３から３０の何れかの数字を表す。） Formula (1)

(In the formula, R ₁ , R ₂ and R ₃ are either H, C _n H _{2n + 1} or OC _n H _{2n + 1} (except when all of R ₁ , R ₂ and R ₃ are H). And n represents any number from 3 to 30.)

Formula (2)

（式中、Ｒ₁，Ｒ₂，Ｒ₃はＨ，Ｃ_nＨ_2n+1又はＯＣ_nＨ_2n+1の何れか（ただし、Ｒ₁，Ｒ₂，Ｒ₃のすべてがＨの場合を除く。）を表し、ｎは３から３０の何れかの数字を表し、ＭはＺｎ，Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｃｄの何れかを表す。） Formula (3)

(In the formula, R ₁ , R ₂ and R ₃ are either H, C _n H _{2n + 1} or OC _n H _{2n + 1} (except when all of R ₁ , R ₂ and R ₃ are H). ), N represents any number from 3 to 30, and M represents any one of Zn, Mn, Fe, Co, Ni, Cu, and Cd.)

Formula (4)

（式中、Ｒ₁，Ｒ₂，Ｒ₃はＨ，Ｃ_nＨ_2n+1又はＯＣ_nＨ_2n+1の何れか（ただし、Ｒ₁，Ｒ₂，Ｒ₃のすべてがＨの場合を除く。）を表し、ｎは３から３０の何れかの数字を表し、ＭはＺｎ，Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｃｄの何れかを表す。） Formula (5)

(In the formula, R ₁ , R ₂ and R ₃ are either H, C _n H _{2n + 1} or OC _n H _{2n + 1} (except when all of R ₁ , R ₂ and R ₃ are H). ), N represents any number from 3 to 30, and M represents any one of Zn, Mn, Fe, Co, Ni, Cu, and Cd.)

Formula (6)

（式中、Ｒ₁，Ｒ₂，Ｒ₃はＨ，Ｃ_nＨ_2n+1又はＯＣ_nＨ_2n+1の何れか（ただし、Ｒ₁，Ｒ₂，Ｒ₃のすべてがＨの場合を除く。）を表し、ｎは３から３０の何れかの数字を表す。） Formula (7)

(In the formula, R ₁ , R ₂ and R ₃ are either H, C _n H _{2n + 1} or OC _n H _{2n + 1} (except when all of R ₁ , R ₂ and R ₃ are H). And n represents any number from 3 to 30.)

Formula (8)

（式中、Ｒ₁，Ｒ₂，Ｒ₃はＨ，Ｃ_nＨ_2n+1又はＯＣ_nＨ_2n+1の何れか（ただし、Ｒ₁，Ｒ₂，Ｒ₃のすべてがＨの場合を除く。）を表し、ｎは３から３０の何れかの数字を表し、ＭはＺｎ，Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｃｄの何れかを表す。） Formula (9)

(In the formula, R ₁ , R ₂ and R ₃ are either H, C _n H _{2n + 1} or OC _n H _{2n + 1} (except when all of R ₁ , R ₂ and R ₃ are H). ), N represents any number from 3 to 30, and M represents any one of Zn, Mn, Fe, Co, Ni, Cu, and Cd.)

Formula (10)

（式中、ＲはＨ，Ｃ_nＨ_2n+1又はＯＣ_nＨ_2n+1の何れか（ただし、Ｒは同一でも互いに異なっていてもよいが、すべてがＨの場合は除く。）を表し、ｎは３から３０の何れかの数字を表す。）で示されるリニアテトラピロール系色素。 Formula (11)

(In the formula, R represents H, C _n H _{2n + 1,} or OC _n H _{2n + 1} (however, R may be the same or different from each other, except when all are H)). , N represents any number from 3 to 30).

Formula (12)

Formula (13)

（式中、ＲはＨ，Ｃ_nＨ_2n+1又はＯＣ_nＨ_2n+1の何れか（ただし、Ｒは同一でも互いに異なっていてもよいが、すべてがＨの場合は除く。）を表し、ｎは３から３０の何れかの数字を表し、ＭはＺｎ，Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｃｄの何れかを表す。）で示されるリニアテトラピロール系色素。 Formula (14)

(In the formula, R represents H, C _n H _{2n + 1,} or OC _n H _{2n + 1} (however, R may be the same or different from each other, except when all are H)). , N represents any number from 3 to 30, and M represents any one of Zn, Mn, Fe, Co, Ni, Cu, and Cd.).

Formula (15)

  These compounds can be synthesized by, for example, (a) complexing tetraphenylporphyrin or octaalkylporphyrin, (b) cleavage by conjugate oxidation of this complex, and (c) complexing of this cleavage product depending on the compound. can do.

Here, the complexation of tetraphenylporphyrin or octaalkylporphyrin in (a) is performed by, for example, chlorinating a phenyl group having a tetraphenylporphyrin having an alkyl group or an alkoxy group or a porphyrin having an alkyl group in an organic solvent such as dimethylformamide. It is carried out by reflux heating with a metal salt such as iron (FeCl ₂ ). The cleavage of the complex of (b) can be performed by, for example, (b1) oxidation by bubbling oxygen gas in the presence of a reducing agent, (b2) crystallization by aqueous sodium tetrafluoroborate, (b3) neutralization by an acid such as hydrochloric acid. To do. In addition, it is possible to produce a cleavage compound having a different structure from the same complex compound by changing the reaction conditions in (b1), specifically, the reaction temperature and the like. Furthermore, the complexation of (c) is performed, for example, by mixing a metal acetate such as lead acetate and copper acetate and a cleavage substance in an organic solvent.

  Note that this synthesis method is merely an example, and the illustration of this synthesis method is not intended to limit the compounds included in the claims of this invention in any way. That is, as long as the chemical structures are the same, the compounds described in the claims may be synthesized by a synthesis method other than the above synthesis method.

  The linear tetrapyrrole dye thus obtained has an alkyl group and an alkoxy group in the phenyl group. And since these alkyl groups and alkoxy groups interact with organic substances and organic solvents, compatibility with organic substances and solubility in organic solvents are improved, and orientation at the inorganic-organic interface is improved.

  Next, in order to clarify the characteristics of the present invention more specifically, a plurality of compounds were produced and their characteristics were examined. The following examples are for better understanding of the present invention, and are not intended to limit the scope of the claims of the present invention in any way.

According to the synthesis scheme shown in FIG. 1, C ₁₂ H ₂₅ O-biladienone Zn complex (Compound 3 and Compound 4) was synthesized. Details thereof will be described below. In addition, in order to clarify the relationship between FIG. 1 and the following description, the same number was assigned to the same compound.

(1) Synthesis of [5,10,15,20-tetrakis (4-dodecyloxyphenyl) porphyrinato] iron (III) chloride (Compound 1)
Distilled dimethylformamide in a 100 ml reaction vessel 50 ml, 5,10,15,20-tetrakis (4-dodecyloxyphenyl) porphyrin 500 mg (3.70 × 10 ^-3 mol), iron (II) chloride n hydrate 1.04 g Each was added and heated to reflux at 160 ° C. for 3 hours with stirring. After completion of the reaction, the reaction solution was cooled to room temperature, 200 ml of chloroform was added thereto and transferred to a separatory funnel, and the organic layer was washed several times with distilled water and 0.05 mol / l hydrochloric acid. The organic layer was dehydrated with sodium sulfate, and then chloroform was distilled off under reduced pressure to obtain black purple crystals. The yield was 497 mg (95.6%), and mass analysis by fast atom bombardment ionization (FAB) confirmed a peak at m / z (mass / valence) of 1405 ([M-Cl] ⁺ ). did it.

(2) Synthesis of C ₁₂ H ₂₅ O-biladienone (compound 2)
250 ml of chloroform saturated with oxygen, 30 ml of pyridine in which Compound 1 (500 mg, 3.47 × 10 ⁻⁴ mol) was dissolved, and 2.5 g of L-(+)-ascorbic acid were added to a 500 ml reaction vessel. After stirring for 1.5 hours at room temperature with oxygen bubbling, the solution was filtered. The filtrate was transferred to a separatory funnel, washed with distilled water and dried over sodium sulfate. Thereafter, what was distilled off under reduced pressure with an evaporator was dissolved again in 12.5 ml of pyridine, an aqueous solution of sodium tetrafluoroborate (125 ml, 1.2 mol / l) was added, and the mixture was stirred for 1 hour while cooling in an ice bath. The filtered product was dissolved again in a mixed solvent of 200 ml of acetone and 35 ml of chloroform, hydrochloric acid (30 ml, 1.5 mol / l) was added, and the mixture was stirred at room temperature for 1 hour. The solution was poured into 600 ml ice water and extracted with dichloromethane. The extract was distilled off under reduced pressure to about 100 ml using an evaporator, transferred to a separatory funnel, washed with distilled water, and dried over sodium sulfate. After distilling off the solvent under reduced pressure, it was purified twice by silica gel column chromatography (first developing solvent was dichloromethane, second developing solvent was dichloromethane: acetone = 99: 1), and C ₁₂ H ₂₅ O-biladienone (Compound 2) was obtained.

The synthesis yield was 96.3 mg (yield 19.6%). In addition, when ¹ H NMR (CDCl ₃ ) spectrum was measured, 0.97 (t, 12H), 1.28-1.50 (m, 72H), 1.75-1.83 (m, 8H), 3.93-4.04 (m, 8H), 6.18 ( m, 3H), 6.32 (s, 1H), 6.39 (d, 1H, J = 4.8 Hz), 6.53 (d, 1H, J = 4 Hz), 6.84-6.99 (m, 11H), 7.30 (m, 2H ), 7.38 (d, 2H, J = 4.8 Hz), 7.49 (d, 2H, J = 8.4 Hz), 7.90 (d, 2H J = 8.8 Hz), 9.90 (br s, 1H), 11.0 (br s, 1H) and 12.3 (br s, 1H) were confirmed. Further, when mass analysis was performed by a fast atom bombardment ionization method (FAB), a peak of m / z (mass / valence) was confirmed at 1384 ([M-OH] ⁺ ). Furthermore, when the absorption spectrum UV-visible (CHCl ₃ ) λ _max of ultraviolet-visible light in chloroform was measured, peaks were confirmed at 323, 379 and 572 nm.

(3) Effect of solvent difference on absorption spectrum In addition, organic solvents containing chloroform, specifically dichloromethane, chloroform, acetone, ethyl ester, 2-propanol, methanol, DMF (N, N-dimethylformamide), hexane The visible light absorption spectra in were compared. The result is shown in FIG. As can be seen from this figure, the color of Compound 2 changed depending on the type of solvent dissolved.

(4) Synthesis of C ₁₂ H ₂₅ O-biladienone Zn complex (compound 3)
20 ml of dehydrated chloroform was added to a 50 ml reaction vessel, and compound 2 (20.4 mg, 1.46 × 10 ⁻⁵ mol) was dissolved therein, and then a saturated zinc acetate methanol solution (4 ml) was added. After stirring at room temperature for 30 minutes, the reaction solution was washed with sodium bicarbonate water and distilled water. After dehydrating the organic layer with sodium sulfate, the solvent was reduced in pressure. The yield of synthesis was 20.0 mg (yield 93.9%), and mass analysis by fast atom bombardment ionization (FAB) showed that m / z (mass / valence) was 1446 (C ₉₂ H ₁₂₅ O ₆ N _{4 The} calculated value for Zn is 1445.9.) Further, when the absorption spectrum UV-visible (CHCl ₃ ) λ _max of ultraviolet-visible light in chloroform was measured, a peak was confirmed at 479 and 812 nm. Compound 3 changed to compound 4 when left in the air.

(5) Effect of metal ion difference on absorption spectrum In addition, a copper complex was synthesized using a saturated copper acetate methanol solution instead of a saturated zinc acetate methanol solution, and its visible light absorption spectrum was measured in chloroform. The results are shown in FIG. 3 together with the visible light absorption spectrum of the zinc complex (Compound 3). As can be seen from this figure, the spectrum of Compound 2, that is, its color, was changed by the coordinated metal ion.

A C ₁₂ H ₂₅ O-bilindinone Mn complex (Compound 6) was synthesized according to the synthesis scheme shown in FIG. Details thereof will be described below. In addition, in order to clarify the relationship between FIG. 4 and the following description, the same number was assigned to the same compound.

(1) Synthesis of C ₁₂ H ₂₅ O-bilindinone (compound 5)
To a 500 ml reaction vessel, 250 ml of chloroform saturated with oxygen, 30 ml of pyridine in which compound 1 (500 mg, 3.47 × 10 ⁻⁴ mol) was dissolved, and 2.5 g of L-(+)-ascorbic acid were added. The mixture was refluxed at 60 ° C. for 1.5 hours with oxygen bubbling, allowed to cool to room temperature, and then filtered. The filtrate was transferred to a separatory funnel and washed with distilled water and dried over sodium sulfate. Thereafter, what was distilled off under reduced pressure with an evaporator was dissolved again in 12.5 ml of pyridine, an aqueous solution of sodium tetrafluoroborate (125 ml, 1.2 mol / l) was added, and the mixture was stirred for 1 hour while cooling in an ice bath. The filtered product was dissolved again in a mixed solvent of 200 ml of acetone and 35 ml of chloroform, hydrochloric acid (30 ml, 1.5 mol / l) was added, and the mixture was stirred at room temperature for 1 hour. The solution was poured into 600 ml ice water and extracted with dichloromethane. The extract was distilled off under reduced pressure to about 100 ml using an evaporator, transferred to a separatory funnel, washed with distilled water, and dried over sodium sulfate. After the solvent was distilled off under reduced pressure, purification was performed twice by silica gel column chromatography (the first developing solvent was dichloromethane, the second developing solvent was dichloromethane: acetone = 99: 1), and compound 5 was obtained.

The synthesis yield was 19.3 mg (5% yield). In addition, when ¹ H NMR (CDCl ₃ ) spectrum was measured, 12.052 (br s, 1H), 8.280 (br s, 2H), 7.486 (ds, 2H), 7.283 (ms, 1H), 6.997 (m, 4H) , 6.857 (d, 4H), 6.857 (d, 2H), 6.815 (d, 2H), 6.212 (d, 2H), 3.867 to 4.046 (m, 6H), 1.690 to 1.857 (m, 6H), 1.247 to 1.523 A signal was confirmed at (m, 54H) and 0.884 (t, 9H). Thus, compound 5 different from compound 2 could be synthesized by changing the reaction temperature when cleaving compound 1 to synthesize the cleavage substance.

(2) Synthesis of C ₁₂ H ₂₅ O-bilindinone Mn complex (Compound 6)
20 ml of dehydrated chloroform was added to a 50 ml reaction vessel, and after dissolving compound 5 (20.4 mg, 1.8 × 10 ⁻⁵ mol), a saturated zinc acetate / methanol solution (4 ml) was added. After stirring at room temperature for 30 minutes, the reaction solution was washed with sodium bicarbonate water and distilled water. The organic layer was dehydrated with sodium sulfate, and the solvent was reduced in pressure. The synthesis yield was 19.0 mg (91% yield).

  According to the synthetic scheme shown in FIG. 5, 2,3,7,8,12,13,17,18-octapentyl-1,19,21,24-tetrahydro-1,19-bilinedione (compound 8a), 2 , 3,7,8,12,13,17,18-octaoctyl-1,19,21,24-tetrahydro-1,19-bilinedione (compound 8b), 2,3,7,8,12,13, 17,18-octaoctyl-1,19,21,24-tetrahydro-1,19-bilinedionato zinc (II) (compound 9) was synthesized and its properties were investigated. Details thereof will be described below. In addition, in order to clarify the relationship between FIG. 5 and the following description, the same number was assigned to the same compound.

(1) Synthesis of Compound 7a Compound 7a was synthesized as follows. Distilled dimethylformamide in a 100 ml reaction vessel 60 ml, 2,3,7,8,12,13,17,18-octapentylporphyrin 80 mg (9.3 × 10 ^-2 mol) and 0.074 g of iron (II) chloride n-hydrate were added, and the mixture was heated to reflux at 160 ° C. for 3 hours with stirring. After completion of the reaction, the reaction solution was cooled to room temperature, 200 ml of chloroform was added thereto and transferred to a separatory funnel, and the organic layer was washed several times with distilled water and 0.05 mol / l hydrochloric acid. The organic layer was dehydrated with sodium sulfate, and then chloroform was distilled off under reduced pressure to obtain dark purple crystals. The yield was 63 mg (73%), and mass analysis by fast atom bombardment ionization (FAB) confirmed a peak at 925 ([M-Cl] ⁺ ) for m / z (mass / valence). did it.

(2) Synthesis of compound 8a
50 ml of chloroform saturated with oxygen, 6 ml of pyridine in which compound 7a (30 mg, 3.1 × 10 ⁻⁵ mol) was dissolved, and 0.3 g of L-(+)-ascorbic acid were added to a 500 ml reaction vessel. After stirring for 30 minutes at room temperature with oxygen bubbling, the solution was filtered. The filtrate was transferred to a separatory funnel, washed with distilled water and dried over sodium sulfate. Thereafter, the solvent distilled off under reduced pressure by an evaporator was dissolved again in 2.5 ml of pyridine, an aqueous sodium tetrafluoroborate solution (25 ml, 1.2 mol / l) was added, and the mixture was stirred for 1 hour while being cooled in an ice bath. The filtrated product was dissolved again in 50 ml of acetone, hydrochloric acid (10 ml, 1.5 mol / l) was added, and the mixture was stirred at room temperature for 1 hour. The solution was poured into 100 ml ice water and extracted with dichloromethane. The extract was distilled off under reduced pressure to about 30 ml using an evaporator, transferred to a separatory funnel, washed with distilled water, and dried over sodium sulfate. After the solvent was distilled off under reduced pressure, purification was performed twice by silica gel column chromatography (the first developing solvent was dichloromethane, the second developing solvent was dichloromethane: acetone = 98: 2) to obtain compound 7a.

The synthesis yield was 5.0 mg (17% yield, converted to porphyrin). Further, when ¹ H NMR (CDCl ₃ ) spectrum was measured, 6.58 (s, 1H), 5.84 (s, 2H), 2.19-2.58 (t, 16H), 1.21-1.60 (m, 48H), 0.9 (t, A signal was confirmed at 24H). Further, when mass analysis was performed by a fast atom bombardment ionization method (FAB), a peak of m / z (mass / charge) was confirmed at 892 (MH ⁺ ).

(3) Synthesis of Compound 7b Compound 7b was synthesized as follows.
Distilled dimethylformamide 60 ml, 2,3,7,8,12,13,17,18-octaoctylporphyrin 173 mg (1.43 × 10 ^-4 mol) and 0.4 g of iron (II) chloride n-hydrate were added, and the mixture was heated to reflux at 160 ° C for 3 hours with stirring. After completion of the reaction, the reaction solution was cooled to room temperature, 200 ml of chloroform was added thereto, transferred to a separatory funnel, and the organic layer was washed several times with distilled water. The organic layer was dehydrated with sodium sulfate, and chloroform was distilled off under reduced pressure to obtain reddish brown crystals. The yield was 180 mg (97%), and mass analysis by fast atom bombardment ionization (FAB) confirmed a peak at 1262 ([M-Cl] ⁺ ) for m / z (mass / valence). did it.

(4) Synthesis of compound 8b
50 ml of chloroform saturated with oxygen, 6 ml of pyridine in which compound 7b (173 mg, 1.4 × 10 ⁻⁴ mol) was dissolved, and 0.5 g of L-(+)-ascorbic acid were added to a 300 ml reaction vessel. After stirring for 30 minutes at room temperature with oxygen bubbling, the solution was filtered. The filtrate was transferred to a separatory funnel, washed with distilled water and dried over sodium sulfate. Thereafter, the solvent distilled off under reduced pressure by an evaporator was dissolved again in 2.5 ml of pyridine, an aqueous sodium tetrafluoroborate solution (25 ml, 1.2 mol / l) was added, and the mixture was stirred for 1 hour while being cooled in an ice bath. The filtrated product was dissolved again in 50 ml of acetone, hydrochloric acid (10 ml, 1.5 mol / l) was added, and the mixture was stirred at room temperature for 1 hour. The solution was poured into 100 ml ice water and extracted with dichloromethane. The extract was distilled off under reduced pressure to about 10 ml using an evaporator, transferred to a separatory funnel, washed with distilled water, and dried over sodium sulfate. After the solvent was distilled off under reduced pressure, purification was performed twice by silica gel column chromatography (the first developing solvent was dichloromethane, the second developing solvent was dichloromethane: acetone = 98: 2) to obtain compound 7a.

The synthesis yield was 28 mg (yield 20%, converted to porphyrin). Further, when ¹ H NMR (CDCl ₃ ) spectrum was measured, as shown in FIG. 6, 6.57 (s, 1H), 5.83 (s, 2H), 2.52-2.19 (t, 24H), 1.29-1.59 (m. 96H) and 0.88 (t, 24H). NH protons could not be confirmed. Furthermore, when mass analysis was performed by a fast atom bombardment ionization method (FAB), as shown in FIG. 7, a peak of m / z (mass / valence) could be confirmed at 1228 (MH ⁺ ).

(3) Effect of difference in solvent on absorption spectrum Compound 8b was compared with visible light absorption spectra in organic solvents containing chloroform, specifically acetone, chloroform, hexane, dichloromethane, and ethyl acetate. The result is shown in FIG. As can be seen from this figure, the color of Compound 8b changed depending on the type of solvent dissolved.

(4) Synthesis of 2,3,7,8,12,13,17,18-octaoctyl-1,19,21,24-tetrahydro-1,19-bilingionatozinc (II) (compound 9)
Chloroform 10 ml was added to a 300 ml reaction vessel, and compound 8b (20 mg, 0.016 mmol) was dissolved therein, and then saturated zinc acetate methanol solution (10 ml) was added. After stirring at room temperature for 10 minutes, the reaction solution was washed with sodium bicarbonate water and distilled water. After dehydrating the organic layer with sodium sulfate, the solvent was dried under reduced pressure.

The synthesis yield was 20 mg (97% yield, converted to vilindione). In addition, when measuring ¹ H NMR (CDCl ₃ ) spectrum, 6.43 (s, 1H), 5.70 (s, 1H), 5.28 (s, 1H), 3.68 (s, 1H), 2.03-2.49 (m, 16H) , 1.16-1.45 (m, 96H), 0.92 (t, 24H). Further, when mass analysis was performed by a fast atom bombardment ionization method (FAB), a peak was confirmed at a position where m / z (mass / valence) was 1290 (MH ⁺ ).

(5) Characteristics of Compounds 8a, 8b and Compound 9 In order to examine whether the compounds 8a, 8b and Compound 9 can be used as liquid crystals, the following characteristics were examined for these compounds.

(5a) Thermal characteristics It was found that Compound 8a is a crystalline substance having a melting point of 90 ° C. As a result of observing this compound with a polarizing microscope, no mesophase was observed.

  By observation with a microscope while heating, it was found that the compound 8b became an opaque liquid from 50 ° C. and a transparent liquid from 81 ° C. The compound 8b was subjected to thermal analysis using a differential scanning calorimeter (DSC). The result is shown in FIG. As can be seen from this figure, Compound 8b showed two small endothermic peaks at 51 ° C. and 71 ° C., and a large endothermic peak at 81 ° C.

  Compound 8b was analyzed by powder X-ray diffraction. The result is shown in FIG. From this result, it was found that the compound 8b had a tetragonal columnar structure in which the distance between the columns was 29.3 mm and the distance between the disks was 4.6 mm. It was also found that the diffraction peak at a low diffraction angle (angle 2θ = 4.2 °) broadens at 51 ° C. and splits into two peaks at 73 ° C. by measuring while increasing the temperature.

  Furthermore, from the observation result with a polarizing microscope, it was found that Compound 8b exhibited a Shrieren structure between 51 and 71 ° C. The result is shown in FIG. 11A is a micrograph of the crystal phase at 25 ° C., and FIG. 11B is a micrograph of the liquid crystal phase at 75 ° C.

  Compound 9 was subjected to thermal analysis using a differential scanning calorimeter (DSC). The result is shown in FIG. As can be seen from this figure, Compound 9 showed large endothermic peaks at 92 ° C and 113 ° C. Further, observation with an optical microscope revealed that Compound 9 liquefied at 92 ° C. From these results, it was found that Compound 9 exhibited a chiral discotic nematic phase between 92 and 113 ° C. and an isotropic liquid phase above 130 ° C.

  Further, Compound 9 was analyzed by powder X-ray diffraction method. As a result, a widely scattered peak was observed at 25 ° C. and 2θ = 4.1 °. This indicates that the crystallinity is very poor at this temperature. In addition, in 52-113 degreeC, since the X-ray-diffraction peak of sufficient resolution was not obtained, it was unknown what kind of phase was shown.

  Finally, the summarized results of calorimetric analysis of compounds 8a, 8b and 9 are shown in Table 1 below.

(5b) Structure and thermal properties of compound 9 Infrared spectra of compound 9 (As prepared) and an annealed product (Annealed) were measured. The result is shown in FIG. The annealing was performed under the condition of heating to 120 ° C., holding for 5 minutes, and then cooling at a rate of 10 ° C./min.

As can be seen from this figure, the ratio of the asymmetric stretching and CH ₂ symmetry stretching of CH _2, i.e. I ₂₉₃₀ / I ₂₈₅₃ is that the of 1.18 in compound 9, is obtained by annealing 1.35 met It was. In general, an increase in the ratio of absorbance from 2930 cm ^-1 to 2850 cm ^-1 means an increase in the number of Gauche types, and thus it was found that annealing increases the number of Gauche types.

Further, from the result of the infrared spectrum measurement, it was found that an equilibrium exists between the lactim type and the lactam type. Compound 9 shows an OH stretch band (see A or B in FIG. 13), whereas compound 9 was annealed and compound 9 was obtained by melting and quickly cooling N. It was found to show a ⁺ H stretch band (see C in FIG. 13). Interestingly, the rapidly cooled sample showed a C = O stretch band at 1692 cm ^-1 , which is due to C = O stretch vibrations with the α position being N ⁺ H --- Zn. .

  These observations indicate that heat treatment reconstitutes compound 9 to stabilize the tetrapyrrole structure, causes isomerization from lactim to lactam, and the conformation of the alkyl chain from the anti-conformation. It was shown to change to the Gauche conformation.

  In addition, molecular orbital calculations were performed on [octamethylbilindionato] zinc, which is a model molecule, to estimate the stability of lactam and lactim types. The molecular orbital calculation program uses Gaussian 98 (Gaussian, Inc., USA), the density functional method uses B3LYP, a kind of density functional (DFT), and 6-31G (D) as the basis function. , A, B and C isomer structures were optimized. The initial structure (assumed structure) used for the molecular orbital calculation is as follows.

  That is, isomers A and B are of the lactam-lactim type, and in isomer A, the hydrogen atom of the OH group is not involved in hydrogen bonding. On the contrary, in isomer B, the hydrogen atom of the OH group was assumed to be involved in hydrogen bonding to lactam nitrogen. In addition, isomer C is a lactam-lactam type, and lactam nitrogen has a hydrogen atom.

  As a result, the energies of isomers A, B, and C were −3194.4549, −3194.4622, and −3194.4609 hartree, respectively. This shows that isomer A is more unstable than isomer B by 4.6 kcal / mol. Also, the energy difference between isomer B and isomer C is only 0.8 kcal / mol, which means that both isomers, i.e., if the molecular aggregation provides additional stabilization energy, i.e. It shows that the lactam-lactim type and the lactam-lactam type are in a solid or liquid crystal state. This indicates that this liquid crystal is a liquid crystal having a new function that can easily change its structure under the influence of a slight external field.

(5c) Impedance characteristics of compound 9 The impedance spectrum of compound 9 was measured with an LCR meter in a state where compound 9 was sandwiched between ITO electrodes (distance between electrodes was 50 μm). The result is shown in FIG. From the Nyquist diagram shown in this figure, it was found that the relaxation frequency was 10 ⁻³ Hz and the relative dielectric constant was 175 between 1 Hz and 100 kHz.

(6) Summary From the above results, it was found that Compound 9 is easily switched by an external field such as an electric field and can be used as a molecular device.

1 is a diagram schematically showing a synthesis scheme of Compound 3 and Compound 4. FIG. It is a graph which shows the relationship between the solvent in which Compound 2 is dissolved, and the visible light absorption spectrum. 3 is a graph showing the relationship between a metal ion coordinated with Compound 2 and a visible light absorption spectrum. 4 is a diagram schematically illustrating a synthesis scheme of Compound 6. FIG. It is the figure which showed the synthetic scheme of the compounds 8 and 9 typically. It is a figure which shows the NMR spectrum of the compound 8b. It is a figure which shows the result (mass spectrum) which mass-analyzed compound 8b. It is a graph which shows the relationship between the solvent in which Compound 8b is dissolved, and the ultraviolet light absorption spectrum. It is a figure which shows the result of having thermally analyzed the compound 8b or the compound 9 with the differential scanning calorimeter (DSC). In addition, (a) shows the result of Compound 8b and (b) shows the result of Compound 9. It is a figure which shows the result of having analyzed the compound 8b by the powder X ray diffraction method. It is a polarization microscope photograph of compound 8b. (A) is a micrograph of the crystal phase at 25 ° C., and (b) is a micrograph of the liquid crystal phase at 75 ° C. It is the result of having measured the infrared spectrum of the compound 9 and what annealed this. 4 is a diagram for explaining the structure of Compound 9. FIG. It is the result (Nyquist diagram) which measured the impedance spectrum of compound 9.

Claims (15)

Formula (1)

(In the formula, R ₁ , R ₂ and R ₃ are either H, C _n H _{2n + 1} or OC _n H _{2n + 1} (except when all of R ₁ , R ₂ and R ₃ are H). ), And n represents any number from 3 to 30.) Formula (2)

The linear tetrapyrrole pigment | dye of Claim 1 shown by these. Formula (3)

(In the formula, R ₁ , R ₂ and R ₃ are either H, C _n H _{2n + 1} or OC _n H _{2n + 1} (except when all of R ₁ , R ₂ and R ₃ are H). ), N represents any number from 3 to 30, and M represents any one of Zn, Mn, Fe, Co, Ni, Cu, and Cd.)). Formula (4)

The linear tetrapyrrole pigment | dye of Claim 3 shown by these. Formula (5)

(In the formula, R ₁ , R ₂ and R ₃ are either H, C _n H _{2n + 1} or OC _n H _{2n + 1} (except when all of R ₁ , R ₂ and R ₃ are H). ), N represents any number from 3 to 30, and M represents any one of Zn, Mn, Fe, Co, Ni, Cu, and Cd.)). Formula (6)

The linear tetrapyrrole pigment | dye of Claim 5 shown by these. Formula (7)

(In the formula, R ₁ , R ₂ and R ₃ are either H, C _n H _{2n + 1} or OC _n H _{2n + 1} (except when all of R ₁ , R ₂ and R ₃ are H). ), And n represents any number from 3 to 30.) Formula (8)

The linear tetrapyrrole pigment | dye of Claim 7 shown by these. Formula (9)

(In the formula, R ₁ , R ₂ and R ₃ are either H, C _n H _{2n + 1} or OC _n H _{2n + 1} (except when all of R ₁ , R ₂ and R ₃ are H). ), N represents any number from 3 to 30, and M represents any one of Zn, Mn, Fe, Co, Ni, Cu, and Cd.)). Formula (10)

The linear tetrapyrrole pigment | dye of Claim 9 shown by these. Formula (11)

(In the formula, R represents H, C _n H _{2n + 1,} or OC _n H _{2n + 1} (however, R may be the same or different from each other, except when all are H)). , N represents any number from 3 to 30). Formula (12)

The linear tetrapyrrole pigment | dye of Claim 11 shown by these. Formula (13)

The linear tetrapyrrole pigment | dye of Claim 11 shown by these. Formula (14)

(In the formula, R represents H, C _n H _{2n + 1,} or OC _n H _{2n + 1} (however, R may be the same or different from each other, except when all are H)). , N represents any number from 3 to 30, and M represents any one of Zn, Mn, Fe, Co, Ni, Cu, and Cd.). Formula (15)

The linear tetrapyrrole pigment | dye of Claim 14 shown by these.

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