JPWO2018155469A1 - Diazachlorin analogs and method for producing the same - Google Patents

Abstract

It is an object of the present invention to provide a diazachlorin analog which causes photoluminescence. A diazachlorin analog having a partial structure represented by any one of formulas (B) to (D) as a skeleton. (Wherein, M is 2H, Zn, Pt, Pd, Mg, Al, Ga, or Au.)

Description

  The present invention relates to a diazachlorin analog that causes photoluminescence such as fluorescence and phosphorescence, and a method for producing the same.

  As a diazachlorin analog, a Ni complex having Ni as a metal element is known (Non-Patent Document 1).

Ayaka Y., Hayato T., Yoshihiro M., Kazushi M., Hiroshi S., Chemo- and Regioselective Reduction of 5,15-Diazaporphyrins Providing Antiaromatic Azaporphyrinoids, Chem. Eur. J. 2016, 22 3956-3961

  By the way, the diazachlorin analog has a chemical structure similar to porphyrin. Compounds that emit fluorescence are present in porphyrin analogs, and if a compound that emits fluorescence can also be obtained for diazacroline analogs, various applications can be expected.

  The diazachlorin analog disclosed in Non-Patent Document 1 does not emit fluorescence, and thus it is an object to be provided to provide a diazachlorin analog capable of generating photoluminescence such as fluorescence or phosphorescence.

  As a result of diligent studies on diazachlorin analogs, the present inventors have found that changing the metal element contained in the diazachlorin analog from Ni to a different element causes photoluminescence such as fluorescence. The following invention was completed.

  That is, the diazachlorin analog of the present invention that solves the above problem is represented by the general formula (1), (2), or (3), and at least one of the emission peaks at a measurement temperature of 25 ° C is in a range of 500 nm to 1200 nm. Produces photoluminescence that exists within.

（式中、Ｚ^１〜Ｚ^１０はそれぞれ独立して選択される置換基で有り、Ｈ、一部乃至全部の水素がＸにて置換されていても良い炭素数１〜２０の炭化水素基、ＯＨ基、アミノ基、アミド基、一部乃至全部の水素がＸにて置換されていても良いフェニル基、ハロゲン、一部乃至全部の水素がＸにて置換されていても良い炭素数１〜２０のアルコキシ基、一部乃至全部の水素がＸにて置換されていても良い含窒素複素環置換基、含硫黄複素環置換基、含酸素複素環置換基、Ｍは、２Ｈ、Ｚｎ、Ｐｔ、Ｐｄ、Ｍｇ、Ａl、Ｇａ又は、Ａｕである。Ｘは炭素数１〜３の炭化水素基、アルコキシ基、ＯＨ基、アミノ基、又は、ハロゲンである。Ｚ^１〜Ｚ^１０から選択される任意の２以上の置換基は互いに結合して環状構造を構成することもできる。一般式（１）〜（３）で表される化合物は同一の又は異なる２つ以上が結合することができる。）

(Wherein, Z ^{1 to} Z ¹⁰ are independently selected substituents; H, a hydrocarbon group having 1 to 20 carbon atoms in which some or all of hydrogen may be substituted by X; An OH group, an amino group, an amide group, a phenyl group in which some or all of the hydrogens may be substituted by X, a halogen, a carbon number of 1 to 1 in which some to all of the hydrogens may be substituted by X, 20 alkoxy groups, nitrogen-containing heterocyclic substituents in which some or all of the hydrogens may be substituted by X, sulfur-containing heterocyclic substituents, oxygen-containing heterocyclic substituents, M is 2H, Zn, Pt , Pd, Mg, Al, Ga or Au, and X is a hydrocarbon group having 1 to 3 carbon atoms, an alkoxy group, an OH group, an amino group, or a halogen, and is selected from Z ^{1 to} Z ^10. Any two or more substituents may be bonded to each other to form a cyclic structure. The same or different two or more compounds represented by the formulas (1) to (3) can be bonded.)

In particular, Z ^{2 to} Z ⁵ and Z ^{7 to} Z ¹⁰ in the general formulas (1) to (3) are H, and the Z ¹ and Z ⁶ are independently selected from the following substituents (X) Preferably.

（式（Ｘ）中のＲ^１〜Ｒ^５、及び、前記一般式（１）〜前記一般式（３）中のＭは、以下の(i)〜(xii)の組み合わせのうちの何れかである。
(i)Ｒ^１、Ｒ^３、及びＲ^５はＭｅ；Ｒ^２及びＲ^４はＨ、Ｍは２Ｈ、
(ii)Ｒ^１、Ｒ^３、及びＲ^５はＭｅ；Ｒ^２及びＲ^４はＨ；ＭはＺｎ、Ｐｔ、Ｐｄ、Ｍｇ、Ｇａ、Ａl、又はＡｕ、
(iii)Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、及びＲ^５はＨ；Ｍは２Ｈ、
(iv)Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、及びＲ^５はＨ；ＭはＺｎ、Ｐｔ、Ｐｄ、Ｍｇ、Ｇａ、Ａl、又はＡｕ、
(v)Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、及びＲ^５はＦ、Ｍは２Ｈ；
(vi)Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、及びＲ^５はＦ；ＭはＺｎ、Ｐｔ、Ｐｄ、Ｍｇ、Ｇａ、Ａl、又はＡｕ、
(vii)Ｒ^１、Ｒ^２、Ｒ^４、及びＲ^５はＨ；Ｒ^３は炭素数１以上のアルキル基、ペルフルオロアルキル基、炭素数１以上のアルコキシ基、又はＯＨ；Ｍ＝２Ｈ、
(viii)Ｒ^１、Ｒ^２、Ｒ^４、及びＲ^５はＨ；Ｒ^３は炭素数１以上のアルキル基、ペルフルオロアルキル基、炭素数１以上のアルコキシ基、又はＯＨ；Ｍ＝Ｚｎ、Ｐｔ、Ｐｄ、Ｍｇ、Ｇａ、Ａl、又はＡｕ、
(ix)Ｒ^１、Ｒ^３、及びＲ^５はＨ；Ｒ^２及びＲ^４は炭素数１以上のアルキル基、ペルフルオロアルキル基、炭素数１以上のアルコキシ基、又はＯＨ；Ｍは２Ｈ、
(x)Ｒ^１、Ｒ^３、及びＲ^５はＭｅ；Ｒ^２及びＲ^４は炭素数１以上のアルキル基、ペルフルオロアルキル基、炭素数１以上のアルコキシ基、又はＯＨ；ＭはＺｎ、Ｐｔ、Ｐｄ、Ｍｇ、Ｇａ、Ａl、又はＡｕ、
(xi)Ｒ^１及びＲ^５はＨ、Ｒ^２、Ｒ^３、及びＲ^４は炭素数１以上のアルキル基、ペルフルオロアルキル基、炭素数１以上のアルコキシ基、又はＯＨ；Ｍは２Ｈ、
(xii)Ｒ^１及びＲ^５はＭｅ；Ｒ^２、Ｒ^３、及びＲ^４は炭素数１以上のアルキル基、ペルフルオロアルキル基、炭素数１以上のアルコキシ基、又はＯＨ；ＭはＺｎ、Ｐｔ、Ｐｄ、Ｍｇ、Ｇａ、Ａl、又はＡｕ。）

(R ^{1 to} R ⁵ in the formula (X) and M in the general formulas (1) to (3) are any of the following combinations of (i) to (xii) is there.
(i) R ¹ , R ³ and R ⁵ are Me; R ² and R ⁴ are H, M is 2H,
(ii) R ¹ , R ³ , and R ⁵ are Me; R ² and R ⁴ are H; M is Zn, Pt, Pd, Mg, Ga, Al, or Au;
(iii) R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are H; M is 2H;
(iv) R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are H; M is Zn, Pt, Pd, Mg, Ga, Al, or Au;
(v) R ¹ , R ² , R ³ , R ⁴ and R ⁵ are F, M is 2H;
(vi) R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are F; M is Zn, Pt, Pd, Mg, Ga, Al, or Au;
(vii) R ¹ , R ² , R ⁴ , and R ⁵ are H; R ³ is an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M = 2H;
(viii) R ¹ , R ² , R ⁴ , and R ⁵ are H; R ³ is an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M = Zn, Pt; Pd, Mg, Ga, Al, or Au,
(ix) R ¹ , R ³ and R ⁵ are H; R ² and R ⁴ are an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M is 2H;
(x) R ¹ , R ³ and R ⁵ are Me; R ² and R ⁴ are an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M is Zn, Pt; Pd, Mg, Ga, Al, or Au,
(xi) R ¹ and R ⁵ are H, R ² , R ³ , and R ⁴ are an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M is 2H;
(xii) R ¹ and R ⁵ are Me; R ² , R ³ and R ⁴ are an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M is Zn, Pt, Pd, Mg, Ga, Al, or Au. )

  Further, the photoluminescence preferably has one or more emission peaks in the following range. When selected from the compound of the general formula (1), it is within the range of 550 to 950 nm at 25 ° C .; When selected from compounds, the range is from 500 to 950 nm at 25 ° C.

  The method for producing a diazachlorin analog which solves the above-mentioned problem is characterized in that a reducing agent is allowed to act on a starting compound having a partial structure represented by the following general formula (A), and , (D) is converted into a diazachlorin analog having a partial structure.

（式（Ａ）〜（Ｄ）中、Ｍは、２Ｈ、Ｚｎ、Ｐｔ、Ｐｄ、Ｍｇ、Ａl、Ｇａ又は、Ａｕである。）

(In the formulas (A) to (D), M is 2H, Zn, Pt, Pd, Mg, Al, Ga, or Au.)

  Particularly, the reducing agent is preferably a hydrazine derivative or a diimide or hydride reducing agent.

  Whether a compound produces photoluminescence cannot be easily predicted, and it would be significant to be able to provide such compounds that do produce photoluminescence.

It is an ultraviolet-visible spectrum (UV-VIS spectrum) about samples S1-S3 in an example. It is a fluorescence spectrum about samples S1-S3 in an example.

  The diazachlorin analog of the present invention and a method for producing the same will be described in detail below based on embodiments.

(Diazachlorin analog)
Among the diazachlorin analogs represented by the general formulas (1) to (3), the use of the diazachlorin analog represented by the general formula (2) is particularly effective in photoluminescence (fluorescence or phosphorescence) on the long wavelength side. And so on). As M in the general formulas (1) to (3), 2H, Mg, Zn, Ga, and Al are preferably used, and 2H, Mg, and Zn are more preferably used.

  In photoluminescence, at least one of the emission peaks at a measurement temperature of 25 ° C. exists in the range of 500 nm to 1200 nm. It is preferable that one or more emission peaks exist in the following wavelength range at a measurement temperature of 25 ° C. When selecting from the compounds of the general formula (1), the range is preferably from 550 to 950 nm, more preferably from 600 to 930 nm, even more preferably from 650 to 900 nm. When selecting from the compounds of the general formula (2), the range is preferably from 700 to 1200 nm, more preferably from 720 to 1150 nm, even more preferably from 750 to 1100 nm. When selecting from the compounds of the general formula (3), the range is preferably from 500 to 950 nm, more preferably from 530 to 900 nm, even more preferably from 550 to 850 nm.

  In these compounds, the peak wavelength of the excitation light that causes photoluminescence is not particularly limited, but is preferably visible light, ultraviolet light, or near-infrared light. In particular, it is preferably in the range of 300 nm to 1200 nm, and more preferably in the range of 400 nm to 1000 nm. As the excitation light, there is usually a wavelength having the highest efficiency, but a semiconductor laser having a peak wavelength at 405 nm, 532 nm, 650 nm, 800 nm, or the like, which is widely used from the viewpoint of cost and availability, should be used. Preferably, the compound has a peak that can be sufficiently excited at these wavelengths for the purpose of. Whether or not excitation is sufficiently possible can be determined by whether or not the intensity of light emission due to the generated photoluminescence is sufficient.

  Further, the diazachlorin analogs represented by the general formulas (1) to (3) of the present invention can have an absorption peak in a range from ultraviolet to near-infrared light. Specifically, it can have one or more absorption peaks in the range of 300 nm to 1100 nm, and more preferably has one or more absorption peaks in the range of 500 nm to 900 nm. The absorption peak when selected from the compounds of the general formula (1) is preferably in the range of 550 to 850 nm, more preferably in the range of 580 to 750 nm, and still more preferably in the range of 600 to 700 nm. The absorption peak when selected from the compounds of the general formula (2) is preferably in the range of 600 to 900 nm, more preferably in the range of 650 to 850 nm, and still more preferably in the range of 700 to 820 nm. The absorption peak when selected from the compounds of the general formula (3) is preferably in the range of 450 to 700 nm, more preferably in the range of 470 to 650 nm, and still more preferably in the range of 500 to 620 nm.

(Method for producing diazachlorin analog)
In the method for producing a diazachlorin analog according to the present embodiment, a reducing agent is allowed to act on a raw material compound having a partial structure represented by the general formula (A), and the compound represented by the general formula (B), (C), or (D) This is a method of converting into a diazachlorin analog having a partial structure represented by the following formula: When the reducing agent acts on the partial structure represented by the general formula (A), the partial structure represented by the general formula (A) is changed to the partial structure represented by the general formulas (B) to (D). Is converted. Although it does not specifically limit as a reducing agent, A hydrazine derivative, a diimide, and a hydride reducing agent can be illustrated. The reaction can be performed, for example, by heating in an appropriate solvent.

(Synthesis) Sample S1: diazachlorin derivative of general formula (1) (wherein Z ^{2 to} Z ⁵ and Z ^{7 to} Z ¹⁰ are H, and Z ¹ and Z ⁶ are substituents (X) Preparation of R ¹ = R ³ = R ⁵ = Me, R ² = R ⁴ = H, M = 2H).

  In a glass reactor, 10,20-dimesityl-5,15-diazaporphyrin (0.025 mmol), p-toluenesulfonic acid hydrazide (0.25 mmol), and potassium carbonate (0.625 mmol) were added, and inert gas replacement was performed. Then, dried and degassed pyridine (10 ml) was added. The mixture was stirred at 100 ° C. for 18 hours under an inert gas atmosphere under light protection. Heating was stopped, the mixture was cooled to room temperature, and pyridine was removed under reduced pressure. Distilled water and ethyl acetate were added to the residue. The organic layer was separated, washed with distilled water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained solid was chromatographed through silica gel. The column was eluted with a mixture of ethyl acetate and hexane (1: 4) to give 12% of sample S1 (diazachlorin).

¹ H NMR (500 MHz, CDCl ₃ ): δ 8.96 (d, J = 8.5 Hz, 1H), 8.71 (d, J = 7.5 Hz, 1H), 8.64 (d, J = 9.0 Hz, 1H), 8.53 ( d, J = 9.0 Hz, 1H), 8.36 (d, J = 7.0 Hz, 1H), 8.33 (d, J = 8.5 Hz, 1H), 7.26 (s, 2H), 7.23 (s, 2H), 4.54- 4.59 (m, 2H), 4.00-4.05 (m, 2H), 2.59 (s, 3H), 2.56 (s, 3H), 1.89 (s, 6H), 1.88 (s, 6H), and -0.50 (s, 2H) ppm; ¹³ C NMR (126 MHz, CDCl ₃ ): δ 175.66, 173.33, 160.41, 151.41, 145.91, 145.21, 141.80, 138.82, 138.37, 138.08, 137.99, 135.85, 135.38, 133.58, 132.68, 132.04, 131.33, 128.99, 128.02, 127.97, 127.88, 126.34, 122.38, 112.80, 35.18, 34.94, 21.38, 21.35, 21.12, and 20.88 ppm; HR-MS (ESI-MS): m / z = 551.2926, calcd for (C ₃₆ H ₃₄ N ₆ ) ⁺ = 551.2918 [(M + H) ⁺ ].

Sample S2: a bacteriodiazachlorin derivative of the general formula (2) (wherein Z2 to Z5 and Z7 to Z10 are H, and Z1 and Z6 are substituents (X). R ¹ = R ^{3 = R 5 = Me, R} 2 = R 4 = H, M = 2H) preparation of.

  In a glass reactor, 10,20-dimesityl-5,15-diazaporphyrin (0.025 mmol), p-toluenesulfonic acid hydrazide (0.25 mmol), and potassium carbonate (0.625 mmol) were added, and inert gas replacement was performed. Then, dried and degassed pyridine (10 ml) was added. The mixture was stirred at 100 ° C. for 18 hours under an inert gas atmosphere under light protection. Heating was stopped, the mixture was cooled to room temperature, and pyridine was removed under reduced pressure. Distilled water and ethyl acetate were added to the residue. The organic layer was separated, washed with distilled water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained solid was chromatographed through silica gel. The column was eluted with a mixture of ethyl acetate and hexane (1: 4) to obtain 48% of sample S2 (bacteriodiazachlorin).

¹ H NMR (500 MHz, CDCl ₃ ): δ 8.53 (d, J = 4.5 Hz, 1H), 7.53 (d, J = 5.0 Hz, 1H), 8.09 (d, J = 4.5 Hz, 1H), 8.09 ( d, J = 5.0 Hz, 1H), 7.22 (s, 4H), 4.42-4.45 (m, 4H), 3.85-3.88 (m, 4H), 2.54 (s, 6H), 1.89 (s, 12H), and -0.69 (s, 2H) ppm; ¹³ C NMR (126 MHz, CDCl ₃ ): δ 169.45, 166.17, 143.91, 138.01, 137.90, 136.30, 135.58, 128.90, 123.95, 123.40, 115.96, 35.29, 33.73, 21.49, and 20.79 ppm; HR-MS (ESI-MS): m / z = 553.3057, calcd for (C ₃₆ H ₃₆ N ₆ ) ⁺ = 553.3074 [(M + H) ⁺ ].

Sample S3: isobacterial diazachlorin derivative of the general formula (3) (wherein Z ^{2 to} Z ⁵ and Z ^{7 to} Z ¹⁰ are H, and Z ¹ and Z ⁶ are substituents (X) Preparation of R ¹ = R ³ = R ⁵ = Me, R ² = R ⁴ = H, M = 2H).

  In a glass reactor, 10,20-dimesityl-5,15-diazaporphyrin (0.025 mmol), p-toluenesulfonic acid hydrazide (0.05 mmol), potassium hydroxide (1.35 mmol) were added, and inert gas replacement was performed. This was followed by the addition of dried and degassed pyridine (10 ml). The mixture was stirred at 100 ° C. for 2 hours under an inert gas atmosphere under light protection. Thereafter, p-toluenesulfonic acid hydrazide (0.25 mmol) was added to the reaction vessel, and the mixture was further stirred for 20 hours. Heating was stopped, the mixture was cooled to room temperature, and pyridine was removed under reduced pressure. Distilled water and ethyl acetate were added to the residue. The organic layer was separated, washed with distilled water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained solid was chromatographed through silica gel. The column was eluted with a mixture of ethyl acetate and hexane (2: 3) to give 25% of sample S3 (Isobacteriodiazachlorin).

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.26-7.30 (m, 4H), 7.11 (s, 2H), 7.05 (s, 2H), 6.44 (s, 2H), 3.57-3.62 (m, 2H) , 3.07-3.12 (m, 2H), 2.46 (s, 3H), 2.41 (s, 3H), 2.05 (s, 6H), and 2.00 (s, 6H) ppm; ¹³ C NMR (126 MHz, CDCl ₃ ) : δ 138.27, 138.02, 137.56, 137.03, 136.87, 135.30, 134.56, 132.37, 129.61, 128.68, 127.84, 119.75, 32.21, 31.51, 21.40, 21.35, 20.44, and 20.24 ppm; ESI-MS: m / z = 553.2997, calcd for (C ₃₆ H ₃₄ N ₆ ) ⁺ = 553.3074 [(M + H) ⁺ ].

(UV-VIS spectrum, fluorescence spectrum measurement)
The UV-VIS spectrum and the fluorescence spectrum of the samples S1 to S3 were measured (solvent: dichloromethane). FIG. 1 shows the results of the UV-VIS spectrum.

  For samples S1 to S3, in order to determine whether or not photoluminescence occurs, high peaks on the long wavelength side are respectively selected from the UV-VIS spectrum (S1: 665.0 nm, S2: 771.5 nm, S3: 557. 0 nm), and the fluorescence spectrum was measured using them as excitation light. FIG. 2 shows the results.

  As is clear from FIG. 2, fluorescence was observed for each of the samples S1 to S3, and the maximum fluorescence wavelength was (S1: 675.5 nm, S2: 778.0 nm, S3: 582.2 nm).

(Relationship between Photoluminescence Properties and Types of M in General Formulas (1) to (3))
Photoluminescence properties of samples S1 to S3 when Zn was introduced as M were evaluated. M was introduced by heating and stirring zinc acetate (II), which is the corresponding metal salt for the samples S1 to S3, in a pyridine solvent at 100 ° C. When the obtained compound was evaluated, it was found that the emission wavelength was shifted by about 20 to 50 nm, and the fluorescence was generated in a state where the fluorescence quantum yield was reduced by 1 to 5%.

  For M, Ga, and Al as M, compounds introduced using salts of the respective elements can be synthesized, and at least fluorescence is generated in the range of 500 nm to 1200 nm. Predicted or confirmed.

  In addition, the properties of photoluminescence when Pt was introduced as M for samples S1 to S3 were evaluated. The introduction of M was performed by subjecting platinum (II) chloride, which is the corresponding metal salt of each of the samples S1 to S3, to reflux stirring in a benzonitrile solvent. When the photoluminescence property of the obtained compound was evaluated, at least phosphorescence was observed in the range of 750 to 950 nm. For Pd and Au as M, compounds introduced by using salts of the respective elements can be synthesized, and it is possible to produce at least phosphorescence within the range of 500 nm to 1200 nm from experimental and other results and theoretical viewpoints. Predicted or confirmed.

  In addition, the properties of photoluminescence when Cu was introduced as M for samples S1 to S3 were evaluated. The introduction of M was carried out by stirring and refluxing copper (II) acetate, which is the corresponding metal salt, in samples S1 to S3 in an N, N'-dimethylformamide solvent. When the properties of the photoluminescence of the obtained compound were evaluated, no light emission was observed. Similarly, a compound of M is Ni disclosed in Non-patent Document 1, and a compound of M is Fe and Co were synthesized in the same manner, and the properties of photoluminescence were evaluated. As a result, no light emission was observed.

Claims (5)

Represented by the general formula (1), (2) or (3),
A diazachlorin analog which causes photoluminescence, wherein at least one of emission peaks at a measurement temperature of 25 ° C. exists in a range of 500 nm to 1200 nm.

(Wherein, Z ^{1 to} Z ¹⁰ are independently selected substituents; H, a hydrocarbon group having 1 to 20 carbon atoms in which some or all of hydrogen may be substituted by X; An OH group, an amino group, an amide group, a phenyl group in which some or all of the hydrogens may be substituted by X, a halogen, a carbon number of 1 to 1 in which some to all of the hydrogens may be substituted by X, 20 alkoxy groups, nitrogen-containing heterocyclic substituents in which some or all of the hydrogens may be substituted by X, sulfur-containing heterocyclic substituents, oxygen-containing heterocyclic substituents, M is 2H, Zn, Pt , Pd, Mg, Ga, Al, or Au, and X is a hydrocarbon group having 1 to 3 carbon atoms, an alkoxy group, an OH group, an amino group, or a halogen, and is selected from Z ^{1 to} Z ^10. Any two or more substituents may be bonded to each other to form a cyclic structure. The same or different two or more compounds represented by the general formulas (1) to (3) can be bonded.) Z ^{2 to} Z ⁵ and Z ^{7 to} Z ¹⁰ in the general formulas (1) to (3) are H,
The diazachlorin analog according to claim 1, wherein Z ¹ and Z ⁶ are independently selected from the following substituents (X).

(R ^{1 to} R ⁵ in the formula (X) and M in the general formulas (1) to (3) are any of the following combinations of (i) to (xii) is there.
(i) R ¹ , R ³ and R ⁵ are Me; R ² and R ⁴ are H, M is 2H,
(ii) R ¹ , R ³ , and R ⁵ are Me; R ² and R ⁴ are H; M is Zn, Pt, Pd, Mg, Ga, Al, or Au;
(iii) R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are H; M is 2H;
(iv) R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are H; M is Zn, Pt, Pd, Mg, Ga, Al, or Au;
(v) R ¹ , R ² , R ³ , R ⁴ and R ⁵ are F, M is 2H;
(vi) R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are F; M is Zn, Pt, Pd, Mg, Ga, Al, or Au;
(vii) R ¹ , R ² , R ⁴ , and R ⁵ are H; R ³ is an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M = 2H;
(viii) R ¹ , R ² , R ⁴ , and R ⁵ are H; R ³ is an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M = Zn, Pt; Pd, Mg, Ga, Al, or Au,
(ix) R ¹ , R ³ and R ⁵ are H; R ² and R ⁴ are an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M is 2H;
(x) R ¹ , R ³ and R ⁵ are Me; R ² and R ⁴ are an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M is Zn, Pt; Pd, Mg, Ga, Al, or Au,
(xi) R ¹ and R ⁵ are H, R ² , R ³ , and R ⁴ are an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M is 2H;
(xii) R ¹ and R ⁵ are Me; R ² , R ³ and R ⁴ are an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M is Zn, Pt, Pd, Mg, Ga, Al, or Au. ) The diazachlorin analog according to claim 1, wherein one or more emission peaks are present in the following range.
When selecting from the compounds of the general formula (1), within the range of 550 to 950 nm at 25 ° C.,
When selecting from the compounds of the general formula (2), within the range of 700 to 1200 nm at 25 ° C.,
When selected from the compounds of the general formula (3), within the range of 500 to 950 nm at 25 ° C. A diazachlorin having a partial structure represented by the following general formula (B), (C) or (D) by allowing a reducing agent to act on a raw material compound having a partial structure represented by the following general formula (A) Method for producing analogs.

(In the formulas (A) to (D), M is 2H, Zn, Pt, Pd, Mg, Al, Ga, or Au.)   The method for producing a diazachlorin analog according to claim 4, wherein the reducing agent is a hydrazine derivative, a diimide or a hydride reducing agent.

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