Antibacterial or antialgal agent

Abstract

To provide a compound capable of maintaining long-term photo-antibacterial or antialgal activity.SOLUTION: An antibacterial or antialgal agent is prepared, which contains, as an active ingredient, a compound represented by the general formula (I) in the figure (where M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si, or Al) or a salt thereof.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to antibacterial or antialgal agents and compounds having antibacterial or antialgal activity. [Background technology]

[0002] As people spend more time at home due to the COVID-19 pandemic, "therapy"—soothing scents and animals (pets)—is becoming popular. Pets have become a particularly popular form of therapy, with sales in 2020 increasing 8.2% from the previous year to approximately 280 billion yen (see Non-Patent Document 1). Globally, the market is predicted to grow at a rate of over 5.0% between now and 2028. Among pets, Aquapets, such as tropical fish, killifish, and goldfish, are expected to continue growing steadily even after the COVID-19 pandemic, due to their low maintenance costs and effort. They rank third, fifth, and sixth, behind dogs and cats, in the rankings of pets people want to keep in the future. Aquapets are also said to be effective in preventing dementia in the elderly. However, Aquapets require weekly water changes, making them difficult to popularize among the elderly.

[0003] To reduce the frequency of water changes in Aquapet tanks, anti-algae solutions containing silver or nitrate bacteria, or pumice stones containing these, are being used. However, these products have problems such as the strong odor of the concentrate, the difficulty of adding a uniform solution due to the settle-out nature of the solution, and the fact that they are not biodegradable.

[0004] Porphyrins, which are found in plants, are not toxic themselves, can be used as fertilizer in small amounts, and are known to be highly biodegradable. Furthermore, these porphyrin compounds are used in the treatment of malignant tumors using photodynamic therapy (PDT) and as tracers in positron emission tomography (PET). The present inventors have conducted research on derivatives of fluorinated porphyrins and fluorinated chlorin porphyrins, and have disclosed various porphyrin derivative compounds, methods for synthesizing these compounds, and their photokilling effects (see Patent Documents 1 and 2, and Non-Patent Documents 2 to 5).

[0005] Furthermore, with regard to porphyrin compounds, a bactericidal effect against Legionella bacteria in outdoor fountains has been disclosed using a complex in which antimony is introduced into the center of a metalloporphyrin (see Non-Patent Document 6). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-30671 [Patent Document 2] International Publication No. 2008 / 102669 Brochure [Non-patent literature]

[0007] [Non-Patent Document 1] Ministry of Economy, Trade and Industry website, Pet Industry Trends - Pet-related industries remain strong even during the COVID-19 pandemic - March 11, 2022 URL: www.meti.go.jp / statistics / toppage / report / minikaisetsu / hitokoto_kako / 20220311hitokoto.html [Non-patent document 2] S.Hirohara, et.al., J. Photochem. Photobiol. B, Biol. 2009, 97, 22-33. [Non-patent document 3] S. Hirohara, et.al J. Med. Chem. 2015, 58, 8658-8670. [Non-patent document 4] M. Obata et al., J. Photochem. Photobiol. B, Biol., 2016, 162, 324-331. [Non-Patent Document 5] Shiho Hirohara et al. Japan Journal of Social Sciences (JJSLMS) Vol. 44, No. 1 (2023) [Non-patent document 6] Masahide Yasuda, Bulletin of the Faculty of Education, Miyazaki International University, "Educational Science Review", No. 7 (2020), pp. 1-9 Summary of the Invention [Problem to be solved by the invention]

[0008] As the number of people keeping aquapets is increasing as described above, there is a need for the development of antibacterial agents for aquapets that can reduce the frequency of water changes in aquarium tanks and make it easier for even elderly people to keep aquapets. However, existing antibacterial agents have short-term effects or contain non-biodegradable substances. Therefore, an object of the present disclosure is to provide a compound that can maintain photoantibacterial or antialgal activity for a long period of time, and to provide an antibacterial or antialgal agent containing such a compound. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above problems, and have used their knowledge of porphyrin chemistry to develop highly photostable fluorinated porphyrins and chlorins, as well as carriers thereof. They have discovered that compounds in which a HOCH2CH2S- group, a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group is bound to the phenyl of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (TFPP) or 5,10,15,20-tetrakis(pentafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorin derivative (TFPC) possess antibacterial or antialgal activity and are photostable, leading to the completion of the present invention.

[0010] That is, the present invention is as follows. [1] General formula (I): [ka] (In the formula, M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si, or Al. X 1 ~X 20 are each independently, fluorine atoms, HOCH2CH2S- group, H(OCH2CH2) nO-group (n represents an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and X 1 ~X 20 At least one selected from HOCH2CH2S- group, H(OCH2CH2) n O-group (n represents an integer of 1 to 100), a 4-pyridinothio group, or It is a 1-methyl-4-pyridinothio group. A is a ring having a structure represented by the following formula (A1), a ring having a structure represented by formula (A2), a ring having a structure represented by formula (A3), a ring having a structure represented by formula (A4), or a ring having a structure represented by formula (A5), B is a ring having a structure represented by the following formula (B1), a ring having a structure represented by formula (B2), a ring having a structure represented by formula (B3), a ring having a structure represented by formula (B4), or a ring having a structure represented by formula (B5), C is a ring having a structure represented by the following formula (C1), a ring having a structure represented by formula (C2), a ring having a structure represented by formula (C3), a ring having a structure represented by formula (C4), or a ring having a structure represented by formula (C5), D is a ring having a structure represented by the following formula (D1), a ring having a structure represented by formula (D2), a ring having a structure represented by formula (D3), a ring having a structure represented by formula (D4), or a ring having a structure represented by formula (D5). wherein the wavy line indicates a binding site.) or a salt thereof as an active ingredient. [ka] [2] The antibacterial or antialgal agent according to [1] above, wherein the compound represented by the general formula (I) is a compound represented by the following formula (II) or formula (III): [ka] (Wherein, M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si, or Al; R 1 ~R 4 are each independently a fluorine atom, a HOCH2CH2S- group, or a H(OCH2CH2) n O- group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and R 1 ~R 4 At least one selected from the group consisting of HOCH2CH2S- group, H(OCH2CH2) n O- group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group. [ka] (Wherein, M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si, or Al; R 1 ~R 4 are each independently a fluorine atom, a HOCH2CH2S- group, or a H(OCH2CH2) n O- group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and R 1 ~R 4 At least one selected from the group consisting of HOCH2CH2S- group, H(OCH2CH2) n O- group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group. [3] The antibacterial or antialgal agent according to [1] or [2] above, wherein M is two hydrogen atoms, Zn, Ni, Gd, or Pd. [4] The above R 1 ~R 4 At least two selected from the above are the same group, and the same group is a HOCH2CH2S- group, a H(OCH2CH2) n The antibacterial or antialgal agent according to the above [2] or [3], wherein the aryl group is an O-group (n represents an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group. [5] The compound represented by formula (I) (I-1) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate zinc(II), (I-2) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate nickel(II), (I-3) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate palladium(II), (I-4) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate gadolinium(III), (I-5) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorin, (I-6) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate palladium(II), (I-7) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate gadolinium(III), (I-8) 5,10,15,20-Tetrakis(4-(2-acetylethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate, zinc(II) (I-9) 5,10,15,20-tetrakis(4-(2-acetylethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate zinc(II), (I-10) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate zinc(II), (I-11) 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin, (I-12) 5,15-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrin, (I-13) 5,10-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrin, (I-14) 5,10,15-tris(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-20-(pentafluorophenyl)porphyrin, (I-15) 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)porphyrin, (I-16) 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate zinc(II), (I-17) 5,15-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrinate zinc(II), (I-18) 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)porphyrinate zinc(II), (I-19) 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate nickel(II), (I-20) 5,15-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrinate nickel(II), (I-21) 5,10-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrinate nickel(II), (I-22) 5,10,15-tris(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-20-(pentafluorophenyl)porphyrinate nickel(II), (I-23) 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)porphyrinate nickel(II), (I-24) 5-(4-(1-methyl-4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin, (I-25) 5-(4-(1-methyl-4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate nickel(II), (I-26) 5-(4-(polyethylene glycol 400)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin, (I-27) 5-(4-(polyethylene glycol 1000)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin, (I-28) 5-(4-(Polyethylene Glycol 4000)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (I-29) 5-(4-(2-hydroxyethoxy)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin, (I-30) 5,15-bis(4-(2-hydroxyethoxy)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrin, (I-31) 5,10-bis(4-(2-hydroxyethoxy)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrin, (I-32) 5,10,15-tris(4-(2-hydroxyethoxy)-2,3,5,6-tetrafluorophenyl)-20-(pentafluorophenyl)porphyrin, (I-33) 5,10,15,20-tetrakis(4-(2-hydroxyethoxy)-2,3,5,6-tetrafluorophenyl)porphyrin, (I-34) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrin, (I-35) 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorin, (I-36) 5,10-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrinate zinc(II), or (I-37) 5,10,15-tris(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-20-(pentafluorophenyl)porphyrinate zinc(II) The antibacterial or antialgal agent according to any one of [1] to [5] above, [6] General formula (IV): [ka] (In the formula, M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si, or Al. X 1 ~X 20 are each independently, Fluorine atom, H(OCH2CH2) n O- group (n represents an integer of 2 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and X 1~X 20 At least one selected from H(OCH2CH2) n O-group (n is an integer of 2 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group. A is a ring having a structure represented by the following formula (A1), a ring having a structure represented by formula (A2), a ring having a structure represented by formula (A3), a ring having a structure represented by formula (A4), or a ring having a structure represented by formula (A5), B is a ring having a structure represented by the following formula (B1), a ring having a structure represented by formula (B2), a ring having a structure represented by formula (B3), a ring having a structure represented by formula (B4), or a ring having a structure represented by formula (B5), C is a ring having a structure represented by the following formula (C1), a ring having a structure represented by formula (C2), a ring having a structure represented by formula (C3), a ring having a structure represented by formula (C4), or a ring having a structure represented by formula (C5), D is a ring having a structure represented by the following formula (D1), a ring having a structure represented by formula (D2), a ring having a structure represented by formula (D3), a ring having a structure represented by formula (D4), or a ring having a structure represented by formula (D5). Here, the wavy line indicates a binding site.) or a salt thereof. [ka] [7] The compound or salt thereof according to [6] above, wherein the compound represented by the general formula (IV) is a compound represented by the following formula (V) or formula (VI): [ka] (Wherein, M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si, or Al; R 1 ~R 4 are each independently a fluorine atom, H(OCH2CH2) n O- group (n is an integer of 2 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and R 1 ~R4 At least one selected from H(OCH2CH2) n O- group (n is an integer of 2 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group. [ka] (Wherein, M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si, or Al; R 1 ~R 4 are each independently a fluorine atom, H(OCH2CH2) n O- group (n is an integer of 2 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and R 1 ~R 4 At least one selected from H(OCH2CH2) n O- group (n is an integer of 2 to 100), a 2-hydroxyethylthio group, a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group. [8] The compound or salt thereof according to [6] or [7] above, wherein M is two hydrogen atoms, Zn, Ni, Gd, or Pd. [Effects of the Invention]

[0011] The compound of the present invention can be used stably for a long period of time as an antibacterial or antialgal agent in water in aquariums, outdoor fountains, toilet drainage, and the like. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a photograph of the surface of TFPP(mEt)3-supported silica gel obtained in the preparation of porphyrin compound-supported silica gel. [Figure 2] FIG. 2 is a graph showing the results of a photosterilization (inactivation) test of porphyrin against E. coli using simulated sunlight (light intensity: 6, 12, 24 J / cm 2 ) in Example 1. [Figure 3]Fig. 3 shows the results of a photosterilization (inactivation) test using Synechocystis sp. PCC 6803 in Example 2. In Fig. 3, (1) represents a system to which solutions of commercially available drugs 1 to 3 were added, (2) represents a system to which TFPP(mEt) solution (final concentration: 1 µM in 1% DMSO / medium) was added, (3) represents a system to which TFPP(mEt) or Zn-TFPP(mEt) solution (final concentration: 10 or 50 µM in 1% DMSO / medium) was added, (4) represents a system to which Zn-TFPP(mEt) solution (final concentration: 5 µM in 1% DMSO / medium) was added, and (5) represents a system to which Zn-TFPP(mEt)-supported silica gel was added. [Figure 4A] 4A shows the results of a photodisinactivation test using Synechocystis sp. PCC 6803 in Example 2. The test results were obtained using porphyrin solutions containing mercaptoethanol derivatives of Zn-TFPP(mEt)4 (Zn-PM4), H2-TFPC(mEt)4 (CM4), and Zn-TFPC(mEt)4 (Zn-CM4) solutions (final concentrations of 5 μM and 1 μM in 1% DMSO / medium, respectively), H2-TFPC(mEt)4-supported silica gel (CM4(Si)), and Zn-TFPC(mEt)4-supported silica gel (Zn-CM4(Si)) (final concentrations of 0.5 μM in 1% DMSO / medium), and vehicle (v) (1% DMSO / CM). [Figure 4B]4B shows the results of a photodisinactivation test using Synechocystis sp. PCC 6803 in Example 2. The test results were obtained using a system containing a porphyrin solution or a chlorin solution, and mercaptoethanol derivatives such as Zn-TFPP(mEt)4-supported silica gel (Zn-PM4(Si)), Zn-TFPC(mEt)4-supported silica gel (Zn-CM4(Si)), TFPP(mEt)4(PM4), TFPC(mEt)4(CM4), Zn-TFPP(mEt)4(Zn-PM4), Zn-TFPC(mEt)4(Zn-CM4), TPPS, Zn-TFPP(mEt)2(Glc)2 (Zn-PM2G2) (final concentration 0.5 μM in 1% DMSO / medium), and vehicle (v) (1% DMSO / CM). [Figure 4C] 4C is a diagram showing the results of a photosterilization (inactivation) test using Synechocystis sp. PCC 6803 in Example 2. FIG. Porphyrin or chlorin solutions, and porphyrin- or chlorin-loaded silica gel solutions, such as pyrimidine derivatives TFPP(S-4Py)4 loaded silica gel (PPy4(Si)), TFPC(S-4Py)4 loaded silica gel (CPy4(Si)), Zn-TFPP(S-4Py)trans-2 loaded silica gel (Zn-PPyt(Si)), TFPP(S-4Py)4(PPy4), Zn-TFPP(S-4Py)1(Zn-PPy1), Zn-TFPP(S-4Py)trans-2(Zn-PPyt), Zn-TFPP(S-4Py)cis-2(Zn-PPyc), Zn-TFPP(S-4Py)3(Zn-PPy3), Zn-TFPP(S-4Py)4(Zn-PPy4), TFPC(S-4Py)4(CPy4), TPPS, These are test results from a system containing TFPP(S-4Py)1 + (PPy1+) (final concentration 0.5 μM in 1% DMSO / medium) and vehicle (v) (1% DMSO / CM). [Figure 5]Figure 5 shows the state of the aquarium two weeks after the photosterilization (inactivation) test in Example 3 was conducted in an aquarium containing waterweed, in a system containing silica gel carrying Zn-TFPP(mEt)4. [Figure 6] FIG. 6 shows the results of a photosterilization test carried out in a pool in Example 5. DETAILED DESCRIPTION OF THE INVENTION

[0013] The contents of all patent and non-patent literature cited herein are hereby incorporated by reference in their entirety.

[0014] In the present specification, examples of the antibacterial or antialgal agent include: The following general formula (I): [ka] (In the formula, M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si, or Al. X 1 ~X 20 are each independently, fluorine atoms, HOCH2CH2S- group, H(OCH2CH2) n O-group (n represents an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and X 1 ~X 20 At least one selected from HOCH2CH2S- group, H(OCH2CH2) n O-group (n represents an integer of 1 to 100), a 4-pyridinothio group, or It is a 1-methyl-4-pyridinothio group. A is a ring having a structure represented by the following formula (A1), a ring having a structure represented by formula (A2), a ring having a structure represented by formula (A3), or a ring having a structure represented by formula (A4): B is a ring having a structure represented by the following formula (B1), a ring having a structure represented by formula (B2), a ring having a structure represented by formula (B3), or a ring having a structure represented by formula (B4), C is a ring having a structure represented by the following formula (C1), a ring having a structure represented by formula (C2), a ring having a structure represented by formula (C3), or a ring having a structure represented by formula (C4): D is a ring having a structure represented by the following formula (D1), a ring having a structure represented by formula (D2), a ring having a structure represented by formula (D3), or a ring having a structure represented by formula (D4). Here, the wavy line indicates the binding site.

[0015] [ka] or a salt thereof as an active ingredient, and hereinafter also referred to as "the antibacterial agent or antialgal agent of the present invention."

[0016] Examples of the compound represented by general formula (I) or a salt thereof include a porphyrin compound represented by the following formula (Ii) or a salt thereof, a chlorin compound represented by the following formula (I-ii) or a salt thereof, a bacteriochlorin compound represented by the following formula (I-iii) or a salt thereof, and an isobacteriochlorin compound represented by the following formula (I-iv) or a salt thereof. Generally, chlorin refers to a macrocyclic compound in which three pyrroles and one pyrroline are connected by four methine groups. Furthermore, a macrocyclic compound in which two pyrroles and two pyrrolines are connected by four methine groups has two isomers, called bacteriochlorin and isobacteriochlorin. An isobacteriochlorin is a compound in which two pyrrolines are adjacent to each other via a methine group. A bacteriochlorin is a compound in which two pyrrolines are positioned opposite each other via an M. [ka] In the chlorin compound represented by the above formula (I-ii) or a salt thereof, A is a ring having the structure represented by the above (A2), (A3), (A4) or (A5). In the bacteriochlorin compound represented by the above formula (I-iii) or a salt thereof, A is a ring having the structure represented by the above (A2), (A3), (A4) or (A5); C is a ring having the structure represented by (C2), (C3), (C4) or (C5). In the isobacteriochlorin compound or salt thereof represented by the above formula (I-iv), A is a ring having the structure represented by the above (A2), (A3), (A4) or (A5); D is a ring having the structure represented by (D2), (D3), (D4) or (D5).

[0017] [The antibacterial or antialgal agent in question] The antibacterial or antialgal agent of the present invention is not particularly limited as long as it contains the compound represented by general formula (I) as an active ingredient, and may be dissolved in a predetermined solution or bound to a carrier. Examples of the predetermined solution include lower C1-6 alcohols such as ethanol, methanol, and propanol, and polyethylene glycols having an average molecular weight of 400 to 4,000. Examples of the carrier include inorganic porous carriers and beads, and examples of inorganic porous carriers include silica gel, zeolite, and soil. Examples of the concentration of the compound represented by general formula (I) relative to the carrier include 0.05 μmol / g to 4 μmol / g, 0.1 μmol / g to 3 μmol / g, 0.2 μmol / g to 2 μmol / g, and 0.25 μmol / g to 1.5 μmol / g. By binding to a carrier, the compound represented by general formula (I) can be further stabilized, and when added to an aquarium, the compound represented by general formula (I) can be made to sink to the bottom of the aquarium, or diffused over the surface or throughout the water in the aquarium, depending on the purpose, resulting in a slow and sustained release. When the water in the aquarium is highly turbid, the compound represented by general formula (I) can be made to float at the top of the aquarium by using a carrier heavy enough to float on the water, thereby enhancing the antibacterial and antialgal effects of light.

[0018] The bacteria that can be treated with the antibacterial agent are not particularly limited, and examples thereof include gram-positive bacteria, gram-negative bacteria, and fungi.

[0019] Examples of the Gram-positive bacteria include Bacillus, Staphylococcus, Streptococcus, Enterococcus, Corynebacterium, Listeria, Clostridium, Eubacterium, methicillin-resistant Staphylococcus aureus, and penicillin-resistant Streptococcus pneumoniae.

[0020] The Gram-negative bacteria that are the target of the antibacterial agent are not particularly limited, but examples thereof include Escherichia bacteria such as Escherichia coli, Legionella bacteria, Pseudomonas bacteria such as Pseudomonas aeruginosa, Salmonella bacteria, Klebsiella bacteria such as Klebsiella pneumoniae, Campylobacter bacteria, and Helicobacter bacteria.

[0021] The fungi that can be treated with the antibacterial agent are not particularly limited, but examples thereof include yeasts such as those of the genus Saccharomyces, fungi of the genus Candida, and fungi of the genus Aspergillus.

[0022] The algae that can be treated with the antialgal agent are not particularly limited, and examples thereof include cyanobacteria (blue-green algae) such as Synechococcales, diatoms, xanthophytes, and dinoflagellates.

[0023] The antibacterial or antialgal agent of the present invention may contain additives suited to the dosage form, such as excipients, disintegrants, binders, thickeners, solvents such as water, ethanol, and 2-propanol, thickeners, isotonicity agents, pH adjusters, lubricants, colorants, antioxidants, flavoring agents, and coating agents.

[0024] The present antibacterial or antialgal agent can be administered to a liquid or solid containing or adhering to the fungi or algae targeted by the antibacterial or antialgal agent. Examples of such liquids include water for raising Aquapets, fountain water, pool water, hot spring or bath water, fish and shellfish farms, water for hydroponic plant cultivation, water in water storage tanks at food factories, toilet wastewater, cleaning wastewater, and disaster drainage. Examples of such solids include aquariums for raising Aquapets, fountains and the surrounding water storage areas, pool walls, walls for hydroponic plant cultivation, the inner walls of water storage tanks at food factories, the surfaces of cleaning equipment, and walls of hot springs or baths. While the present antibacterial or antialgal agent exerts its antibacterial or antialgal activity upon exposure to light, it does not necessarily need to be used in a location where sunlight can be irradiated. It can be used indoors or, even indoors without sunlight, in an environment where light such as LED or fluorescent light can be irradiated. The light irradiation time is 3 to 30 J / cm. 2 , 6~24J / cm2 , 10-15J / cm 2 Examples include:

[0025] When the present antibacterial or antialgal agent is used, it can be added so that the concentration of the compound represented by general formula (I) as the active ingredient is 0.3 to 80 μM, 0.5 to 70 μM, 1 to 50 μM, or 2 to 20 μM.

[0026] [Compound represented by general formula (I)] In the compound represented by general formula (I), X 1 ~X 20 are each independently a fluorine atom, a HOCH2CH2S- group, or a H(OCH2CH2) n O- group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and X 1 ~X 20 At least one selected from the group consisting of HOCH2CH2S- group, H(OCH2CH2) n O- group (n is an integer of 1 to 100), 4-pyridinothio group, or 1-methyl-4-pyridinothio group, but at least one of the four phenyl groups bonded to the porphyrin ring or chlorin ring is not bonded to the o-, m-, or p-position with a HOCH2CH2S- group, H(OCH2CH2) n Preferably, each phenyl group has two or more, three or more, or up to four HOCH2CH2S- groups, H(OCH2CH2) n O- group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group may be bonded, and one, two or more, three or more, or about four phenyl groups bonded to the porphyrin ring or the chlorin ring may have one, two or more, three or more, or four HOCH2CH2S- group, H(OCH2CH2) nO- group (n is an integer of 1 to 100), 4-pyridinothio group, or 1-methyl-4-pyridinothio group may be bonded. In the two phenyl groups bonded to the porphyrin ring or the chlorin ring, at least one HOCH2CH2S- group, H(OCH2CH2) n When an O-group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group is bonded, the configuration of the two phenyl groups may be cis or trans. Here, in this specification, "cis" refers to a compound having substituents attached to the 5th and 10th meso positions of the dye ring, and "trans" refers to a compound having substituents attached to the 5th and 15th meso positions of the dye ring.

[0027] The compounds represented by general formula (I) include X 1 ~X 4 two, three, or four selected from the above are the same groups, and the same groups are not selected from the group consisting of HOCH2CH2S- group, H(OCH2CH2) n O- group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group. 1 ~X 20 In the formula, HOCH2CH2S- group, H(OCH2CH2) n A position other than an O-group (n represents an integer of 1 to 100), a 4-pyridinothio group, and a 1-methyl-4-pyridinothio group is preferably a fluorine atom, and the inclusion of many fluorine atoms can improve the stability of the compound itself.

[0028] The compound represented by the above formula (I) includes X 1 ~X 4 In at least one selected from the group consisting of HOCH2CH2S- group, H(OCH2CH2) n Preferred are an O- group (n represents an integer of 1 to 100), a 4-pyridinothio group, and a 1-methyl-4-pyridinothio group, and preferred are compounds represented by the following formula (II) or (III).

[0029] [ka]

[0030] (Wherein, M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si, or Al; R 1 ~R 4 are each independently a fluorine atom, a HOCH2CH2S- group, or a H(OCH2CH2) n O- group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and R 1 ~R 4 At least one selected from the group consisting of HOCH2CH2S- group, H(OCH2CH2) n O- group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group.

[0031] [ka]

[0032] (Wherein, M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si, or Al; R 1 ~R 4 are each independently a fluorine atom, a HOCH2CH2S- group, or a H(OCH2CH2) n O- group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and R 1 ~R 4 At least one selected from the group consisting of HOCH2CH2S- group, H(OCH2CH2) n O- group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group.

[0033] In the compound represented by the above formula (II) or (III), R 1 , R 2, R 3 and R 4 At least two, preferably three, more preferably four selected from the following may be the same group; 1 , R 2 , R 3 and R 4 At least two, preferably three, more preferably four selected from the above are the same groups, and the same groups are not selected from the group consisting of HOCH2CH2S- group, H(OCH2CH2) n Examples include an O- group (n represents an integer of 1 to 100), a 4-pyridinothio group, and a 1-methyl-4-pyridinothio group.

[0034] Specific examples of the compound represented by formula (I) include: (I-1) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(mEt)4), (I-2) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(mEt)4), (I-3) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate palladium(II) (Pd-TFPP(mEt)4), (I-4) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate gadolinium(III) (Gd-TFPP(mEt)4), (I-5) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorin (TFPC(mEt)4), (I-6) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate palladium(II) (Pd-TFPC(mEt)4), (I-7) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate gadolinium(III) (Gd-TFPC(mEt)4), (I-8) 5,10,15,20-tetrakis(4-(2-acetylethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(AcmEt)4), (I-9) 5,10,15,20-tetrakis(4-(2-acetylethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate zinc(II) (Zn-TFPC(AcmEt)4), (I-10) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate zinc(II) (Zn-TFPC(mEt)4), (I-11) 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(S-4py)1), (I-12) 5,15-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrin (TFPP(S-4py) trans-2 ), (I-13) 5,10-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrin (TFPP(S-4py) cis-2 ), (I-14) 5,10,15-tris(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-20-(pentafluorophenyl)porphyrin (TFPP(S-4py)3), (I-15) 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)porphyrin (TFPP(S-4py)4), (I-16) 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(S-4py)1), (I-17) 5,15-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(S-4py) trans-2 ), (I-18) 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(S-4py)4), (I-19) 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4py)1), (I-20) 5,15-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4py) trans-2 ), (I-21) 5,10-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4py) cis-2 ) (I-22) 5,10,15-tris(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-20-(pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4py)3), (I-23) 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4py)4), (I-24) 5-(4-(1-methyl-4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(S-4Py + -Me)1), (I-25) 5-(4-(1-methyl-4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4Py + -Me)1), (I-26) 5-(4-(polyethylene glycol 400)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(PEG 400 )1), (I-27) 5-(4-(polyethylene glycol 1000)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(PEG 1000 )1), (I-28) 5-(4-(polyethylene glycol 4000)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(PEG 4000 )1) (I-29) 5-(4-(2-hydroxyethoxy)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(EG)1), (I-30) 5,15-bis(4-(2-hydroxyethoxy)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrin (TFPP(EG) trans-2 ), (I-31) 5,10-bis(4-(2-hydroxyethoxy)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrin (TFPP(EG) cis-2 ), (I-32) 5,10,15-tris(4-(2-hydroxyethoxy)-2,3,5,6-tetrafluorophenyl)-20-(pentafluorophenyl)porphyrin (TFPP(EG)3), (I-33) 5,10,15,20-tetrakis(4-(2-hydroxyethoxy)-2,3,5,6-tetrafluorophenyl)porphyrin (TFPP(EG)4), (I-34) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrin (TFPP(mEt)4), (I-35) 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorin, (I-36) 5,10-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrinate zinc(II), or (I-37) 5,10,15-tris(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-20-(pentafluorophenyl)porphyrinate zinc(II) The above polyethylene glycol 400, polyethylene glycol 1000, and polyethylene glycol 4000 refer to substituents obtained by reacting a dye ring with polyethylene glycol having an average molecular weight of 400, 1000, or 4000, respectively.

[0035] [Compound represented by general formula (IV)] In the compound represented by general formula (IV), X 1 ~X 20 are each independently a fluorine atom, H(OCH2CH2) n O- group (n is an integer of 2 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and X 1 ~X 20 At least one selected from H(OCH2CH2) n O-group (n is an integer of 2 to 100), 4-pyridinothio group, or 1-methyl-4-pyridinothio group, but at least one of the o-, m-, and p-positions of the four phenyl groups bonded to the porphyrin ring or chlorin ring is not H(OCH2CH2) n O-group (n is an integer of 2 to 100), 4-pyridinothio group, or 1-methyl-4-pyridinothio group may be bonded. In addition, in each phenyl group, two or more, three or more, or about four H(OCH2CH2) n O- group (n is an integer of 2 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group may be bonded, and one, two or more, three or more, or about four phenyl groups bonded to the porphyrin ring or the chlorin ring may have one, two or more, three or more, or four HOCH2CH2S- group, H(OCH2CH2) n An O-group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group may be bonded to the porphyrin ring or the chlorin ring. At least one of the two phenyl groups bonded to the porphyrin ring or the chlorin ring is H(OCH2CH2). n When an O-group (n is an integer of 2 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group is bonded, the two phenyl groups may be in a cis or trans configuration.

[0036] The compound represented by the general formula (IV) includes X 1 ~X 4 are the same group, and the same group is H(OCH2CH2) nO- group (n is an integer of 2 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group. 1 ~X 20 In H(OCH2CH2) n It is preferable that a position other than an O-group (n represents an integer of 2 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group is a fluorine atom, and the inclusion of many fluorine atoms can improve the stability of the compound itself.

[0037] The compound represented by the above formula (IV) includes X 1 ~X 4 In at least one of the above, H(OCH2CH2) n Preferred are an O- group (n represents an integer of 2 to 100), a 4-pyridinothio group, and a 1-methyl-4-pyridinothio group, and preferred are compounds represented by the following formula (V) or (VI).

[0038] [ka]

[0039] (Wherein, M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si, or Al; R 1 ~R 4 are each independently a fluorine atom, H(OCH2CH2) n O- group (n is an integer of 2 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and R 1 ~R 4 At least one selected from H(OCH2CH2) n O- group (n is an integer of 2 to 100), a 2-hydroxyethylthio group, a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group.

[0040] [ka] (Wherein, M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si, or Al; R 1 ~R 4 are each independently a fluorine atom, H(OCH2CH2) n O- group (n is an integer of 2 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and R 1 ~R 4 At least one selected from H(OCH2CH2) n O- group (n is an integer of 2 to 100), a 2-hydroxyethylthio group, a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group.

[0041] In the compound represented by the above formula (V) or formula (VI), R 1 , R 2 , R 3 and R 4 At least two, preferably three, more preferably four selected from the group consisting of H(OCH2CH2) n Examples include an O- group (n represents an integer of 2 to 100), a 4-pyridinothio group, and a 1-methyl-4-pyridinothio group.

[0042] Specific examples of the compound represented by formula (IV) include: (IV-1) 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(S-4py)1), (IV-2) 5,15-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrin (TFPP(S-4py) trans-2 ), (IV-3) 5,10-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrin (TFPP(S-4py) cis-2 ), (IV-4) 5,10,15-tris(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-20-(pentafluorophenyl)porphyrin (TFPP(S-4py)3), (IV-5) 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)porphyrin (TFPP(S-4py)4), (IV-6) 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(S-4py)1), (IV-7) 5,15-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(S-4py) trans-2 ), (IV-8) 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(S-4py)4), (IV-9) 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4py)1), (IV-10) 5,15-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4py) trans-2 ), (IV-11) 5,10-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4py) cis-2 ), (IV-12) 5,10,15-tris(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-20-(pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4py)3), (IV-13) 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4py)4), (IV-14) 5-(4-(1-methyl-4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(S-4Py + -Me)1), (IV-15) 5-(4-(1-methyl-4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4Py + -Me)1), (IV-16) 5-(4-(polyethylene glycol 400)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(PEG 400 )1), (IV-17) 5-(4-(polyethylene glycol 1000)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(PEG 1000 )1), or (IV-18) 5-(4-(polyethylene glycol 4000)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(PEG 4000 )1) can be mentioned.

[0043] [Compounds represented by general formula (I) or general formula (IV)] The following provides common explanations for the compounds represented by general formula (I) or general formula (IV). In the formula, M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si, or Al, preferably M is two hydrogen atoms, Zn, Ni, Gd, or Pd, more preferably M is Zn or Ni.

[0044] In general formula (I), A is a ring having a structure represented by the following formula (A1), a ring having a structure represented by formula (A2), a ring having a structure represented by formula (A3), or a ring having a structure represented by formula (A4): B is a ring having a structure represented by the following formula (B1), a ring having a structure represented by formula (B2), a ring having a structure represented by formula (B3), or a ring having a structure represented by formula (B4), C is a ring having a structure represented by the following formula (C1), a ring having a structure represented by formula (C2), a ring having a structure represented by formula (C3), or a ring having a structure represented by formula (C4): D is a ring having a structure represented by the following formula (D1), a ring having a structure represented by formula (D2), a ring having a structure represented by formula (D3), or a ring having a structure represented by formula (D4).

[0045] [ka]

[0046] A1, B1, C1, or D1 has a dihydrogen atom bonded to the β-pyrrole position; A2, B2, C2, or D2 has a tetrahydrogen atom bonded to the β-pyrrole position; A3, B3, C3, or D3 has methano(N-methyl)iminomethano bonded to the β-pyrrole position; A4, B4, C4, or D4 has a benzene bonded to the β-pyrrole position, A5, B5, C5, or D5 has naphthalene bonded to the β-pyrrole position. The end of "N-" in the above A2 to D2 represents CH3. The ring may be a porphyrin ring in which A, B, C, and D are A1, B1, C1, and D1, respectively. The ring may also be an isobacteriochlorin ring in which two adjacent rings, specifically, A and B, B and C, C and D, or D and A, are each one of A2 to 5 and B2 to 5, one of B2 to 5 and C2 to 5, one of C2 to 5 and D2 to 5, or one of D2 to 5 and A2 to 5. The ring may also be a bacteriochlorin ring in which two opposing rings, specifically, A and C, or B and D, are each one of A2 to 5 and C2 to 5, or one of B2 to 5 and D2 to 5.

[0047] The salts used herein are not particularly limited, and examples thereof include hydrohalide salts such as hydrochloride and hydrobromide; lower alkylsulfonates such as methanesulfonate, trifluoromethanesulfonate and ethanesulfonate; allylsulfonates such as benzenesulfonate and p-toluenesulfonate; organic acid salts such as fumarate, succinate, citrate, tartrate, oxalate and maleate; and amino acid salts such as glutamate and aspartate.

[0048] [Method for producing a compound represented by general formula (I) or general formula (IV)] The compound represented by general formula (I) or general formula (IV) or a salt thereof can be produced by a known production method using a known compound or a commercially available product as a raw material.

[0049] 1. Preparation of M-TFPP(mEt) M-TFPP(mEt)4 can be produced, for example, by the production method shown in Scheme 1 below, but the present invention is not limited thereto.

[0050] Scheme 1: M-TFPP(mEt)4 [ka]

[0051] The production method represented by Scheme 1 comprises the step of reacting M-TFPP with 2-mercaptoethanol and a weak base catalyst such as diisopropylamine, diethylamine, or triethylamine in a solvent to introduce a substituent into the para-position of the pentafluorophenyl group. M-TFPP can be produced by known methods such as those described in Non-Patent Documents 3 and 4. The solvent is not particularly limited as long as it allows the desired reaction to proceed, and examples include basic solvents such as N,N-dimethylformamide (DMF), formamide, and acetamide, as well as dimethyl sulfoxide (DMSO).

[0052] The amount of 2-mercaptoethanol to be added may be determined depending on the number of phenyl groups to which 2-mercaptoethanol is to be linked among the four pentafluorophenyl groups in M-TFPP. For example, to produce a monosubstituted 2-mercaptoethanol, 1 to 1.5 equivalents of 2-mercaptoethanol and 1 to 2 equivalents of diisopropylamine can be used relative to M-TFPP; to produce a disubstituted 2-mercaptoethanol, 2 to 2.5 equivalents of 2-mercaptoethanol and 2 to 3 equivalents of diisopropylamine can be used relative to M-TFPP; to produce a trisubstituted 2-mercaptoethanol, 3 to 3.5 equivalents of 2-mercaptoethanol and 3 to 4 equivalents of diisopropylamine can be used relative to M-TFPP; and to produce a tetrasubstituted 2-mercaptoethanol, 4 to 4.5 equivalents of 2-mercaptoethanol and 4 to 5 equivalents of diisopropylamine can be used relative to M-TFPP. The amount of M-TFPP is not particularly limited as long as it is 1 equivalent or more relative to diisopropylamine and the desired reaction proceeds, but is usually 1 equivalent or more and 5 equivalents or less.

[0053] 2. Preparation of M-TFPC(mEt)4 M-TFPC(mEt)4 can be produced, for example, by the production method shown in Scheme 2 below, although the present invention is not limited thereto.

[0054] Scheme 2: M-TFPC(mEt)4 [ka]

[0055] The production method represented by Scheme 2 comprises the step of reacting M-TFPC with 2-mercaptoethanol and diisopropylamine in a solvent to introduce a substituent at the para-position of the pentafluorophenyl group. M-TFPC can be produced by known methods, such as those described in Non-Patent Documents 3 and 4. The solvent is not particularly limited as long as it allows the desired reaction to proceed, and examples include basic solvents such as N,N-dimethylformamide (DMF), formamide, and acetamide, as well as dimethyl sulfoxide (DMSO).

[0056] The amount of 2-mercaptoethanol to be added can be determined depending on the number of phenyl groups to which 2-mercaptoethanol is to be linked among the four pentafluorophenyl groups in M-TFPC. For example, to produce monosubstituted 2-mercaptoethanol, 1 to 1.5 equivalents of 2-mercaptoethanol and 1 to 2 equivalents of diisopropylamine can be used relative to M-TFPC; to produce disubstituted 2-mercaptoethanol, 2 to 2.5 equivalents of 2-mercaptoethanol and 2 to 3 equivalents of diisopropylamine can be used relative to M-TFPC; to produce trisubstituted 2-mercaptoethanol, 3 to 3.5 equivalents of 2-mercaptoethanol and 3 to 4 equivalents of diisopropylamine can be used relative to M-TFPC; and to produce tetrasubstituted 2-mercaptoethanol, 4 to 4.5 equivalents of 2-mercaptoethanol and 4 to 5 equivalents of diisopropylamine can be used relative to M-TFPC. The amount of M-TFPC is not particularly limited as long as it is 1 equivalent or more relative to diisopropylamine and the desired reaction proceeds, but is usually 1 equivalent or more and 5 equivalents or less.

[0057] 3.M-TFPP(S-4Py) s Manufacturing M-TFPP(S-4Py) s can be produced, for example, by the production method shown in Scheme 3 below, but the present invention is not limited thereto. The subscript s above is an integer of 1 to 4.

[0058] Scheme 3: M-TFPP(S-4Py) s [ka]

[0059] The production method represented by Scheme 3 comprises a step of reacting M-TFPP with 4-mercaptopyridine and diisopropylamine in a solvent. M-TFPP can be produced by known methods such as those described in Non-Patent Documents 3 and 4. The solvent is not particularly limited as long as it allows the desired reaction to proceed, and examples thereof include basic solvents such as N,N-dimethylformamide (DMF), formamide, and acetamide, as well as dimethyl sulfoxide (DMSO).

[0060] The amount of 2-mercaptoethanol to be added may be determined depending on the number of phenyl groups to which 4-mercaptopyridine is to be linked among the four pentafluorophenyl groups in M-TFPP. For example, to produce a 4-mercaptopyridine mono-substituted compound, 1 to 1.5 equivalents of 4-mercaptopyridine and 1 to 2 equivalents of diisopropylamine can be used relative to M-TFPP; to produce a 4-mercaptopyridine di-substituted compound, 2 to 2.5 equivalents of 4-mercaptopyridine and 2 to 3 equivalents of diisopropylamine can be used relative to M-TFPP; to produce a 4-mercaptopyridine tri-substituted compound, 3 to 3.5 equivalents of 4-mercaptopyridine and 3 to 4 equivalents of diisopropylamine can be used relative to M-TFPP; and to produce a 4-mercaptopyridine tetra-substituted compound, 4 to 4.5 equivalents of 4-mercaptopyridine and 4 to 5 equivalents of diisopropylamine can be used relative to M-TFPP. The amount of M-TFPP is not particularly limited as long as it is 1 equivalent or more relative to diisopropylamine and the desired reaction proceeds, but is usually 1 equivalent or more and 5 equivalents or less.

[0061] 4.M-TFPP(S-4Py + -Me) s Manufacturing M-TFPP(S-4Py + -Me) s can be produced, for example, by the production method shown in Scheme 4 below, but the present invention is not limited thereto.

[0062] Scheme 4 (M-TFPP(S-4Py + -Me) s ) [ka]

[0063] The production method shown in Scheme 4 is M-TFPP(S-4Py) s The production method includes a step of reacting M-TFPP(S-4Py) with methyl iodide in a solvent.s can be produced by known methods in addition to the method described in Scheme 3. The solvent is not particularly limited as long as the desired reaction proceeds, and examples thereof include basic solvents such as N,N-dimethylformamide (DMF), formamide, and acetamide, as well as dichloromethane, chloroform, and dimethyl sulfoxide (DMSO).

[0064] The amount of 4-mercaptopyridine added is M-TFPP(S-4Py) s The amount of methyl iodide can be determined depending on the number of phenyl groups to which methyl iodide is to be linked among the four pentafluorophenyl groups in the formula (1). For example, when producing a monosubstituted methyl iodide, 1 to 5 equivalents of methyl iodide can be used relative to TFPP(S-4Py)1, when producing a disubstituted methyl iodide, 2 to 10 equivalents of methyl iodide can be used relative to TFPP(S-4Py)2, when producing a trisubstituted methyl iodide, 3 to 15 equivalents of methyl iodide can be used relative to M-TFPP(S-4Py)3, ​​and when producing a tetrasubstituted methyl iodide, 4 to 20 equivalents of methyl iodide can be used relative to M-TFPP(S-4Py)4. M-TFPP(S-4Py) s The amount of is not particularly limited as long as it is 1 equivalent or more relative to methyl iodide and the target reaction proceeds, but is usually 1 equivalent or more and 20 equivalents or less.

[0065] The temperature at which the reactions of the above schemes 1 to 4 are carried out is not particularly limited as long as the desired reaction proceeds, but is usually from 0° C. to 150° C. or below the boiling point of the solvent.

[0066] The time for carrying out the reactions of the above schemes 1 to 4 is not particularly limited as long as the desired reaction proceeds, but is usually from 10 minutes to 72 hours.

[0067] 5. M-TFPP(PEG 400~4000 )1 Production M-TFPP(PEG 400~4000) 1 can be produced, for example, by the production method shown in Scheme 5 below, but the present invention is not limited thereto.

[0068] <Scheme 5> (M-TFPP(PEG 400~4000 )1) [ka]

[0069] The production method represented by Scheme 5 comprises a step of reacting M-TFPP with polyethylene glycol having an average molecular weight of 400 to 4000 and potassium tert-butoxide in a solvent. M-TFPP can be produced by known methods such as those described in Non-Patent Documents 3 and 4. The solvent is not particularly limited as long as it allows the desired reaction to proceed, and examples thereof include basic solvents such as N,N-dimethylformamide (DMF), formamide, and acetamide, as well as dimethyl sulfoxide (DMSO).

[0070] The amount of polyethylene glycol with an average molecular weight of 400 to 4000 to be added is 1 to 20 equivalents relative to M-TFPP. (PEG 400~4000 The amount of )1 is not particularly limited as long as it is 1 equivalent or more relative to polyethylene glycol and the target reaction proceeds, but is usually 1 equivalent or more and 10 equivalents or less.

[0071] The temperature at which the reaction of the above Scheme 5 is carried out is not particularly limited as long as the desired reaction proceeds, but is usually −25° C. or higher and 25° C. or lower.

[0072] The time for carrying out the reaction of the above Scheme 5 is not particularly limited as long as the desired reaction proceeds, but is usually from 15 minutes to 48 hours.

[0073] As a post-treatment for the reactions in Schemes 1 to 5, a separation operation or a reprecipitation method can be performed by adding water or an appropriate aqueous solution to the reaction mixture. In the case of Scheme 5, the reaction can be stopped by adding water, followed by distillation of the solvent and washing with an organic solvent to obtain the target product. When using an aqueous solution, a weakly acidic aqueous solution containing hydrochloric acid or the like; saline solution, etc. can be optionally used. During the separation operation, it is possible to add a water-immiscible solvent, such as a benzene-based solvent such as toluene, xylene, benzene, or chlorobenzene; an ester-based solvent such as ethyl acetate, isopropyl acetate, or butyl acetate; a halogen-based solvent such as dichloromethane, dichloroethane, or chloroform; or a hydrocarbon-based solvent such as dichloromethane, chloroform, hexane, heptane, cyclohexane, or methylcyclohexane. These solvents can be used alone or in combination of two or more in any ratio. The number of separations is not particularly limited and can be performed depending on the desired purity or yield. Furthermore, a separation operation is not essential for this reaction.

[0074] The reaction mixture containing the compound obtained above can be dehydrated with a drying agent such as sodium sulfate or magnesium sulfate, but this is not essential.

[0075] The reaction mixture containing the compound obtained above can be subjected to solvent distillation under reduced pressure as long as the compound is not decomposed.

[0076] The reaction mixture containing the compound obtained after distilling off the solvent can be purified with an appropriate solvent by washing, column chromatography, gel permeation chromatography, reprecipitation, recrystallization, etc. Furthermore, each substitution product can be separated and purified by column chromatography using silica gel and a GPC column for the number of substitutions, and by column chromatography using flash silica gel for the difference in arrangement. [Example]

[0077] The present invention will be described in more detail below with reference to examples. The examples are not limiting.

[0078] [Compound synthesis] As the compounds represented by the above general formula (I) or general formula (IV), the compounds shown in the following Tables 1 and 2 were synthesized.

[0079] [Table 1]

[0080] [Table 2]

[0081] [Compound Synthesis 1] Synthesis of 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(mEt)4) 5,10,15,20-Tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrinate zinc(II) (Zn-TFPP, 378 mg, 364 μmol), 2-mercaptoethanol (130 μL, 1860 μmol), and diisopropylamine (260 μL, 1855 μmol) were dissolved in N,N-dimethylformamide (DMF, 40 mL) and stirred overnight at room temperature in the dark. The reaction mixture was dissolved in CHCl / AcOEt (1:1, v / v, ca. 100 mL) and separated with saturated brine (ca. 100 mL × 3). After evaporation of the solvent, the crude product was separated by silica gel column chromatography (silica, φ = 63-210 μm, eluent; gradient from CHCl:AcOEt:(acetone / MeOH) = 1:1:0 to 1:1:small amount (v / v / v)) to obtain the target fraction. After evaporation of the solvent, the residue was purified by flash silica gel column chromatography (silica, φ = 40-50 μm, eluent; CHCl:AcOEt:(acetone / MeOH) = 1:1:small amount (v / v / v)). After evaporation of the solvent, a purple powder was obtained in 48.3% yield.

[0082] [ka]

[0083] 1 H NMR (499.91 MHz, CDCl3 / CD3OD = 5 / 1 (v / v), Si(CH3)4= 0 ppm): δ(ppm) = 8.9430 (8H, brs, β-pyrroleH), 4.0067 (8H, t, 3 J= 6.15 Hz, CH2OH), 3.4883 (4H, brs, OH), 3.4189 (8H, 3 J = 6.20 Hz, SCH2). 19F NMR (470.34 MHz, CDCl3 / CD3OD (= 5:1, v / v), CF3CO2H= -76.5 ppm): δ (ppm)= -128.7567 (8F, dd, 3 J F-F = 25.30 Hz, 5 J F-F = 12.04 Hz, 3,5-PhF Et ), -131.6833 (8F, dd, 3 J = 25.30 Hz, 5 J = 12.04 Hz, 2,6-PhF mEt ). 13 C NMR(125.72 MHz, (CD3)2CO, (CH3)2CO = 29.8 ppm): δ (ppm)= 149.6662 (4-PhC), 147.6462-147.5211, 147.1588-147.0203 (3,5-PhC), 145.6964-145.5599, 145.2242-145.0421 (2,6-PhC), 131.4219 (1-PhC), 121.8512-121.5174 (α-pyrroleC), 115.2374-114.9150 (β-pyrroleC), 104.1721 (mesoC), 61.1702 (S-CH2), 37.0480 (CH2OH). Purity ( 1 H qNMR, 3,5-bis(trifluoromethyl)benzoic acid): 95.5 wt% (Zn-TFPP(mEt)4·3H2O).

[0084] [Compound Synthesis 2] Synthesis of 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(mEt)4) Using a similar method to that for Zn-TFPP(mEt), 5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP, 155 mg, 150 μmol), 2-mercaptoethanol (106 μL, 751 μmol), and diisopropylamine (58 μL, 1855 μmol) were mixed. The reaction mixture was dissolved in CHCl / AcOEt (1:1, v / v, ca. 100 mL) and separated with saturated brine (ca. 100 mL × 3). After distilling off the solvent, the crude product was separated by silica gel column chromatography (silica, φ=63-210 μm, eluent; gradient from CHCl:AcOEt:(acetone / MeOH) = 1:1:0 to 1:1:small amount (v / v / v)) to obtain the target fraction. After distilling off the solvent, the residue was purified by flash silica gel column chromatography (silica, φ=40-50 μm, eluent; CHCl:hexane = 8:2, v / v). After distilling off the solvent, a reddish-brown powder was obtained in 53.9% yield.

[0085] [ka]

[0086] 1 H NMR (499.91 MHz, CDCl3 / CD3OD (= 5 / 1, v / v), Si(CH3)4= 0 ppm): δ(ppm) = 8.8406 (8H, brs, β-pyrroleH), 3.9712 (8H, 3 J = 6.17 Hz, CH2OH), 3.5011 (4H, brs, OH), 3.3842 (8H, 3 J = 6.70 Hz, SCH2). 19F NMR (470.34 MHz, CDCl3 / CD3OD (= 5 / 1, v / v), CF3CO2H= -76.5 ppm): δ (ppm)= -131.2690 (8F, dd, 3 J F-F = 24.88 Hz, 5 J F-F = 12.46 Hz, 3,5-PhF Et ), -134.5191 (8F, dd, 3 J = 24.46 Hz, 5 J = 12.04 Hz, 2,6-PhF mEt ). 13 C NMR (125.72 MHz, (CD3)2CO, (CH3)2CO = 29.8 ppm): δ (ppm)= 147.6178-147.5078, 146.7031-146.6017 (3,5-PhC), 145.6547-145.6107, 144.7784-144.6210 (2,6-PhC), 142.6333 (4-PhC), 132.4499 (1-PhC), 119.0611-118.7539 (α-pyrroleC), 116.1876-115.8671 (β-pyrroleC), 103.6638 (mesoC), 61.1303 (S-CH2), 36.8735 (CH2OH).

[0087] [Compound Synthesis 3] Synthesis of 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate palladium (II) (Pd-TFPP(mEt)4) Using the synthesis method for Zn-TFPP(mEt), 5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrinate palladium(II) (Pd-TFPP, 50.5 mg, 46.8 μmol), 2-mercaptoethanol (14.7 μL, 210.6 μmol), and diisopropylamine (29.8 μL, 210.6 μmol) were reacted and then separated. After evaporation of the solvent, the crude product was separated by silica gel column chromatography (silica, φ = 63-210 μm, eluent; gradient from CHCl:AcOEt:(acetone / MeOH) = 1:1:0 to 1:1:small amount (v / v / v)) to obtain the desired fraction. After distilling off the solvent, the residue was purified by flash silica gel column chromatography (silica, φ = 40-50 μm, eluent; CHCl: AcOEt: (acetone / MeOH) = 6:4: small amount (v / v / v)), and the solvent was distilled off to give a red powder in a 50.0% yield.

[0088] [ka]

[0089] 1 H NMR (499.92 MHz, (CD3)2CO, (CH3)2CO = 2.04 ppm): δ (ppm) = 9.300 (8H, brs, β-pyrroleH), 4.235 (4H, t, 3 J = 5.70 Hz, -OH), 3.997 (8H, q, 3 J = 5.95 Hz, -CH2OH), 3.414 (8H, t, 3 J = 6.35 Hz, -SCH2-). 19 F NMR (470.34 MHz, (CD3)2CO, CF3CO2H = -76.55 ppm): δ (ppm) = -133.89 (8H, dd, 3 JF-F = 25.87 Hz, 5 J F-F = 12.23 Hz, 2,6-PhF), -138.477 (8H, dd, 3 J F-F = 25.40 Hz, 5 J F-F = 12.23 Hz, 3,5-PhF). 13 C NMR (125.72 MHz, (CD3)2CO, (CH3)2CO = 29.8 ppm): δ (ppm) = 149.150, 149.129, 149.017, 148.230, 148.111, 147.223, 147.185, 147.162, 147.075, 146.275, 146.243, 146.151, 142.760, 132.979, 132.911, 120.302, 120.148, 119.998, 117.846, 117.682, 117.519, 107.493, 62.523, 62.408, 38.134, 38.113. UV-vis (c = 5.00 μM, DMSO, path length = 1 cm, 37°C): λ / nm (ε × 10 -3 / M -1 cm -1 ) = 410 (397.0), 518 (39.86), 551 (25.16). Purity (HPLC): >99%.

[0090] [Compound Synthesis 4] Synthesis of 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate gadolinium (III) (Gd-TFPP(mEt)4) Using the synthesis method for Zn-TFPP(mEt), 5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrinate gadolinium(III) (Gd-TFPP, 31.2 mg, 27.6 μmol), 2-mercaptoethanol (13.0 μL, 186.0 μmol), and diisopropylamine (26.3 μL, 185.8 μmol) were reacted and then separated. After evaporation of the solvent, the crude product was separated by silica gel column chromatography (silica, φ = 63-210 μm, eluent; gradient from CHCl:AcOEt:(acetone / MeOH) = 1:1:0 to 1:1:small amount (v / v / v)) to obtain the desired fraction. After distilling off the solvent, the residue was purified by flash silica gel column chromatography (silica, φ = 40-50 μm, eluent; CHCl: AcOEt: (acetone / MeOH) = 6:4: small amount (v / v / v)), and the solvent was distilled off to give a pink powder in a yield of 38.4%.

[0091] [ka]

[0092] 1 H NMR (499.92 MHz, (CD3)2CO, (CH3)2CO = 2.04 ppm): δ (ppm) = 9.009 (8H, brs, β-pyrroleH), 4.242 (4H, t, 3 J = 5.71 Hz, -OH), 3.988 (8H, q, 3 J = 5.71 Hz, -CH2OH), 3.410 (8H, t, 3 J = 6.30 Hz, -SCH2-). 19F NMR (470.34 MHz, (CD3)2CO, CF3CO2H = -76.55 ppm): δ (ppm) = -133.89 (8H, m, 2,6-PhF), -138.477 (8H, dd, m, 3,5-PhF).

[0093] [Compound Synthesis 5] Synthesis of 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorin (TFPC(mEt)4) Using the synthesis method for Zn-TFPP(mEt)4, 5,10,15,20-tetrakis(pentafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorin (TFPC, 106.9 mg, 103.6 μmol), 2-mercaptoethanol (38.0 μg, 544.7 μmol), and diisopropylamine (75.0 μL, 531.4 μmol) were reacted and then separated. After evaporation of the solvent, the crude product was separated by silica gel column chromatography (silica, φ = 63-210 μm, eluent; CHCl : AcOEt : (acetone / MeOH) = 6 : 4 : small amount (v / v / v)) to obtain the desired fraction. After distilling off the solvent, the residue was purified by flash silica gel column chromatography (silica, φ = 40-50 μm, eluent; CHCl : AcOEt : (acetone / MeOH) = 6 : 4 : small amount (v / v / v)), and the solvent was distilled off to give a deep green powder in a yield of 39.8%.

[0094] [ka]

[0095] 1 H NMR (499.91 MHz, CDCl3 / CD3OD (=5 / 1), Si(CH3)4= 0 ppm): δ (ppm) = 8.772 (2H, d,3 J= 4.80 Hz, 12,13-β-pyrroleH), 8.529 (2H, s, 8,17-β-pyrroleH), 8.459 (2H, m, 7,18-β-pyrroleH), 5.291 (2H, brs, 2,3-β-pyrroleH), 3.983 (8H, m, -CH2OH), 3.380 (8H, q, 3 J = 6.00 Hz, -SCH2-), 3.182 (2H, brs, N-CHH), 2.509 (2H, brs, N-CHH), 2.221 (3H, s, N-CH3). 19 F NMR (470.34 MHz, CDCl3 / CD3OD =5 / 1, CF3CO2H = -76.55 ppm): δ (ppm) = -134.662 (1H, dd, 3 J F-F = 24.83 Hz, 5 J F-F = 5.74 Hz, 2,6-PhF), -134.962 (1H, dd, 3 J F-F = 25.73 Hz, 5 J F-F = 11.43 Hz, 2,6-PhF), -135.985 (2H, m, 2,6-PhF), -138.099 (1H, dd, 3 J F-F = 25.87 Hz, 5 J F-F = 11.15 Hz, 3,5-PhF), -139.401 (2H, m, 3,5-PhF), -140.01 (1H, dd, 3 J F-F = 25.72 Hz, 5 J F-F = 12.37 Hz, 3,5-PhF). 13C NMR (125.72 MHz, (CD3)2CO, (CH3)2CO = 29.8 ppm): δ (ppm) = 167.811, 152.340, 148.414, 148.266, 147.574, 146.109, 145.601, 144.867, 144.116, 139.733, 134.724, 132.243, 132.148, 127.916, 123.837, 120.296, 120.233, 120.062, 116.110, 115.645, 106.793, 97.408, 62.500, 61.487, 53.793, 49.079, 40.0971, 37.073, 36.906. UV-vis (c = 5.00 μM, DMSO, path length = 1 cm, 37°C): λ / nm (ε × 10 -3 / M -1 cm -1 ) = 413 (396.0), 505 (25.10), 601 (12.50), 652 (57.40).

[0096] [Compound Synthesis 6] Synthesis of 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate palladium(II) (Pd-TFPC(mEt)4) Using the synthesis method for Zn-TFPP(mEt), 5,10,15,20-tetrakis(pentafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate palladium(II) (Pd-TFPC, 21.1 mg, 18.6 μmol), 2-mercaptoethanol (5.8 μL, 83.6 μmol), and diisopropylamine (12.2 μL, 83.6 μmol) were reacted. The reaction solution was dissolved in CHCl / AcOEt (1:1, v / v, ca. 50 mL) and separated with saturated brine (ca. 50 mL × 3). After distilling off the solvent, the crude product was separated by silica gel column chromatography (silica, φ=63-210 μm, CHCl: AcOEt: (acetone / MeOH) = 6:4: small amount (v / v / v)) to obtain the target fraction. After distilling off the solvent, the residue was purified by flash silica gel column chromatography (silica, φ=40-50 μm, eluent; CHCl: AcOEt: (acetone / MeOH) = 6:4: small amount (v / v / v)). After distilling off the solvent, a blue powder was obtained in 85.8% yield.

[0097] [ka]

[0098] 1 H NMR (499.91 MHz, CDCl3 / CD3OD (= 5 / 1, v / v), Si(CH3)4= 0 ppm): δ (ppm) = 8.4659 (2H, d, 3 J= 4.85 Hz, 8,17-β-pyrroleH), 8.4307 (2H, s, 12,13-β-pyrroleH), 8.1636 (2H, d, 3J = 3.65 Hz, 7,18-β-pyrroleH), 5.28443 (2H, brs, 2,3-β-pyrroleH), 3.9742 (8H, m, -CH2OH), 3.3834 (8H, m, -SCH2-), 3.1496 (2H, t, 3 J= 7.30 Hz, N-CHH), 2.5336 (2H, t, 3 J= 7.32 Hz, N-CHH), 2.2241 (3H, s, N-CH3). 19 F NMR (470.34 MHz, CDCl3 / CD3OD =5 / 1, CF3CO2H = -76.55 ppm): δ (ppm) = -133.0408 (1H, m, 2,6-PhF mEt ), -133.4574 (1H, m, 2,6-PhF), -134.1640 (2H, m, 2,6-PhF mEt ), -135.8072 (1H, m, 3,5-PhF mEt ), -137.5579 (2H, m, 3,5-PhF mEt ), -138.1225 (1H, m, 3,5-PhF mEt ). 13C NMR (125.72 MHz, CDCl3 / CD3OD =5 / 1, CDCl3= 77.0 ppm): δ (ppm)= 155.7445 (1,4,11,14-α-pyrroleC), 148.3323-147.8012 (3,5-PhC), 146.0468-145.4323 (9,16-α-pyrroleC), 145.4323 (4-PhC), 144.8955-144.0572 (2,6-PhC), 138.5018, 137.7147 (6,19-α-pyrroleC), 131.6927 (8,17-β-pyrroleC), 127.7154 (12,13-β-pyrroleC), 127.0591 (7,18-β-pyrroleC), 115.0493 (1-PhC), 109.6305 (10,15-mesoC), 98.2940 (5,20-mesoC), 63.5127 (N-CH2-), 61.4814, 61.2594 (S-CH2), 50.6722 (2,3-β-pyrroleC), 41.0048 (N-CH3), 37.9947, 37.8999 (CH2OH). UV-vis (c = 5.00 μM, DMSO, path length = 1 cm, 37 °C): λ / nm (ε × 10 -3 / M -1 cm -1 ) = 408 (144.4), 491 (11.46), 564 (13.96), 605 (55.76). Purity (HPLC): 98.5%.

[0099] [Compound Synthesis 7] Synthesis of 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate gadolinium(III) (Gd-TFPC(mEt)4) Using the synthesis method for Zn-TFPP(mEt), 5,10,15,20-tetrakis(pentafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate gadolinium(III) (Gd-TFPC, 3.9 mg, 3.4 μmol), 2-mercaptoethanol (1.5 μL, 21.5 μmol), and diisopropylamine (3.1 μL, 21.9 μmol) were reacted. The reaction solution was dissolved in CHCl / AcOEt (1:1, v / v, ca. 50 mL) and separated with saturated brine (ca. 50 mL × 3). After distilling off the solvent, the crude product was separated by silica gel column chromatography (silica, φ=63-210 μm, CHCl: AcOEt: (acetone / MeOH) = 6:4: small amount (v / v / v)) to obtain the target fraction. After distilling off the solvent, the residue was purified by flash silica gel column chromatography (silica, φ=40-50 μm, eluent; CHCl: AcOEt: (acetone / MeOH) = 6:4: small amount (v / v / v)). After distilling off the solvent, a blue powder was obtained in 17.6% yield.

[0100] [ka]

[0101] 1 H NMR (499.91 MHz, CDCl3 / CD3OD (= 4 / 1), Si(CH3)4= 0 ppm): δ (ppm) = 8.516 (2H, d, 3 J= 4.60 Hz, 12,13-β-pyrroleH), 8.382 (2H, s, 8,17-β-pyrroleH), 8.118 (2H, d, 3J= 4.75 Hz, 7,18-β-pyrroleH), 5.155 (2H, brs, 2,3-β-pyrroleH), 4.001 (8H, m, -CH2OH), 3.843 (8H, m, -SCH2-), 3.083 (2H, brs, N-CHH), 2.946 (2H, brs, N-CHH), 2.289 (3H, s, N-CH3). 19 F NMR (470.34 MHz, CDCl3 / CD3OD (= 4 / 1), CF3CO2H = -76.55 ppm): δ (ppm) = -134.86 (1F, m, 2,6-PhF), -135.10 (1F, m, 2,6-PhF), -135.98 (1F, m, 2,6-PhF), -136.49 (1F, m, 2,6-PhF), -137.79 (1F, m, 3,5-PhF), -139.88 (2H, m, 3,5-PhF), -140.029 (1H, m, 3,5-PhF).

[0102] [Compound Synthesis 8] Synthesis of 5,10,15,20-tetrakis(4-(2-acetylethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(AcmEt)4) 5,10,15,20-Tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(mEt)4, 219 mg, 172 μmol), sodium acetate (60 mg, 731 μmol), and acetic anhydride (10 mL, 1.05 mmol) were added and the mixture was stirred for 105 minutes in the dark. o The mixture was heated and stirred at RT for 10 min. CHCl (100 mL) was added to the solution, and the mixture was separated with saturated aqueous sodium bicarbonate (ca. 100 mL × 2) and then water (100 mL). The resulting organic layer was evaporated, and the crude product was purified by silica gel column chromatography (silica, φ = 63-210 μm, eluent; CHCl: AcOEt = 5.5:4.5). The solvent was evaporated to give a pink powder quantitatively.

[0103] [ka]

[0104] 1 H NMR (499.91 MHz, CDCl3, Si(CH3)4= 0 ppm): δ (ppm) = 9.0200 (8H, brs, β-pyrroleH), 4.4316 (8H, d, 3 J= 6.37 Hz, -CH2OH), 3.4547 (8H, d, 3 J= 6.37 Hz, -SCH2-), 2.1120 (12H, s, CH3). 19 F NMR (470.34 MHz, CDCl3, CF3CO2H = -76.55 ppm): δ (ppm) = -134.6130 (8F, dd, 3 J F-F = 25.26 Hz, 5 J F-F = 11.90 Hz, 3,5-PhF Et ), -137.5609 (8F, dd, 3 J = 24.81 Hz, 5 J = 12.39 Hz, 2,6-PhF mEt ). 13 C NMR (125.72 MHz, CDCl3, CDCl3= 77.0 ppm): δ (ppm) = 170.745, 149.905, 132.036, 114.964, 104.902, 62.984, 33.211, 31.918, 29.689, 29.649, 22.687, 20.722, 14.117. Purity (HPLC): >99%.

[0105] [Compound Synthesis 9] Synthesis of 5,10,15,20-tetrakis(4-(2-acetylethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate zinc(II) (Zn-TFPC(AcmEt)4) 5,10,15,20-Tetrakis(4-(2-acetylethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(AcmEt)4) (248 mg, 189 μmol), N-methylglycine (ca. 200 mg, 2400 μmol), and paraformaldehyde (ca. 200 mg, 6700 μmol) were added to toluene (50 mL) and incubated in the dark for 105 minutes. o The mixture was heated and stirred at 37°C. Every 2 hours, ca. 200 mg of N-methylglycine (ca. 200 mg, 2400 μmol) and ca. 200 mg of paraformaldehyde were added, and the mixture was heated and stirred for a total of 12 hours. After evaporation of the solvent, the crude product was purified by silica gel column chromatography (silica, φ = 63-210 μm, eluent; CHCl: hexane: acetone = 7:3: small amount (v / v / v)). After evaporation of the solvent, the residue was purified by flash silica gel column chromatography (silica, φ = 63-210 μm, eluent; CHCl: hexane: acetone = 7:3: small amount (v / v / v)). After evaporation of the solvent, a blue powder (3.9%) was obtained.

[0106] [ka]

[0107] 1 H NMR (499.91 MHz, CDCl3 / CD3OD (= 10 / 1, v / v), Si(CH3)4= 0 ppm): δ (ppm) = 8.5148 (2H, d, 3 J= 3.15 Hz, 8,17-β-pyrroleH), 8.3854 (2H, brs, 12,13-β-pyrroleH), 8.1192 (2H, d, 3 J = 2.35 Hz, 7,18-β-pyrroleH), 5.1640 (2H, brs, 2,3-β-pyrroleH), 4.4385 (8H, ddd,3 J = 13.37 Hz, 3 J = 6.82 Hz, 5 J = 1.90 Hz, CH2OH), 3.4282 (8H, ddd, 3 J = 8.12 Hz, 3 J = 6.35 Hz, 5 J = 2.00 Hz, -SCH2-), 2.8885 (2H, brs, N-CHH), 2.2872 (2H, brs, N-CHH), 2.1691, 2.1615, 2.1568 (3H, s, N-CH3). 19 F NMR (470.34 MHz, CDCl3 / CD3OD =10 / 1, CF3CO2H = -76.55 ppm): δ (ppm) = -133.0408 (1H, m, 2,6-PhF mEt ), -133.4574 (1H, m, 2,6-PhF), -134.1640 (2H, m, 2,6-PhF mEt ), -135.8072 (1H, m, 3,5-PhF mEt ), -137.5579 (2H, m, 3,5-PhF mEt ), -138.1225 (1H, m, 3,5-PhF mEt ). 13 C NMR (125.72 MHz, CDCl3 / CD3OD (= 10 / 1), CDCl3= 77.0 ppm): δ (ppm) = 171.007, 153.323, 147.602, 146.942, 146.601, 146.506, 146.081, 145.950, 131.818, 128.053, 122.092, 118.674, 113.944, 95.918, 63.040, 62.614, 41.210, 33.005, 29.492, 20.488. Purity (HPLC): >99%.

[0108] [Compound Synthesis 10] Synthesis of 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate zinc(II) (Zn-TFPC(mEt)4) 5,10,15,20-Tetrakis(4-(2-acetylethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate zinc(II) (Zn-TFPC(AcmEt)4, 10.1 mg, 7.4 μmol) was added to CHCl / methanol (= 1 / 1 (v / v), ca. 50 mL). Sodium methoxide was added to this mixture to adjust the pH to 9, and the mixture was incubated in the dark for 50 minutes. o The mixture was heated and stirred at RT for 10 min at RT. Acetic acid was added to the reaction mixture to neutralize it, and the solvent was then distilled off. The crude product was purified by silica gel column chromatography (silica, φ = 63-210 μm, eluent; CHCl: hexane: acetone = 7:3: small amount (v / v / v)), and the solvent was distilled off to obtain a blue powder (8.1%).

[0109] [ka]

[0110] 1 H NMR (499.91 MHz, CDCl3 / CD3OD (= 5 / 1), Si(CH3)4= 0 ppm): δ (ppm) = 8.519 (2H, d, 3 J= 4.50 Hz, 12,13-β-pyrroleH), 8.382 (2H, s, 8,17-β-pyrroleH), 8.127 (2H, d, 3J= 4.00 Hz, 7,18-β-pyrroleH), 5.157 (2H, brs, 2,3-β-pyrroleH), 3.951 (8H, m, -CH2OH), 3.861 (8H, m, -SCH2-), 3.050 (2H, brs, N-CHH), 2.944 (2H, brs, N-CHH), 2.276 (3H, s, N-CH3). 19 F NMR (470.34 MHz, CDCl3 / CD3OD (= 5 / 1), CF3CO2H = -76.55 ppm): δ (ppm) = -135.14 (1F, m, 2,6-PhF), -135.602 (1F, m, 2,6-PhF), -136.48 (1F, dd, 3 J F-F = 19.28 Hz, 5 J F-F = 7.53 Hz, 2,6-PhF), -136.67 (1F, dd, 3 J F-F = 24.46 Hz, 5 J F-F = 16.46 Hz, 2,6-PhF), -137.97 (1F, 3 J F-F = 20.69 Hz, 5 J F-F = 11.76 Hz, 3,5-PhF), -139.74 (2H, m, 3,5-PhF), -140.192 (1H, m, 3,5-PhF). 13 C NMR (125.72 MHz, CDCl3 / CD3OD (= 10 / 1), CDCl3= 77.0 ppm): δ (ppm) = 153.013, 146.225, 145.718, 131.501, 126.498, 95.686, 60.823, 50.511, 36.323. UV-vis (c = 5.00 μM, DMSO, path length = 1 cm, 37°C): λ / nm (ε × 10 -3 / M -1 cm -1) = 421 (344.3), 522 (13.32), 587 (15.22), 622 (54.7). Purity (HPLC): >99%.

[0111] [Synthesis of Compounds 11, 12, 13] 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(S-4py)1), 5,15-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrin (TFPP(S-4py)2) trans-2 ), 5,10-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrin (TFPP(S-4py) cis-2 ) synthesis 5,10,15,20-Tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrin (TFPP, 585 mg, 601 μmol), 4-mercaptopyridine (67 mg, 601 μmol), and diisopropylamine (126 μL, 902 μmol) were dissolved in DMF (40 mL) and stirred overnight at room temperature in the dark. The reaction mixture was dissolved in CHCl / AcOEt (1:1, v / v, ca. 200 mL) and separated with saturated brine (ca. 200 mL × 3). After evaporation of the solvent, the crude product was separated by silica gel column chromatography (silica, φ = 63-210 μm, eluent; gradient from CHCl:AcOEt:MeOH = 1:1:0 to 8:0:2 (v / v / v)) to obtain solutions of each substituted isomer. After distilling off the solvent, each substituted product was purified by preparative gel permeation chromatography (GPC, eluent: CHCl3), and the solvent was distilled off to obtain TFPP(S-4Py)1 and TFPP(S-4Py). trans-2 and TFPP(S-4Py) cis-2 The reddish-brown powders were obtained in yields of 28.2%, 7.9% and 11.9%, respectively.

[0112] [Chemical formula]

[0113] TFPP(S-4py)1 1 1H NMR (499.91 MHz, CDCl3, Si(CH3)4 = 0 ppm): δ(ppm) = 8.9502 (4H, d, 3 J = 5.20 Hz, 3,7,13,17-β-pyrroleH), 8.9223 (4H, brs, 2,8,12,18-β-pyrroleH), 8.6601 (2H, brs, 3,5-PyH), 7.3716 (2H, brs, 2,6-PyH), -2.8790 (2H, brs, inner pyrroleH). 1 1H NMR (499.91 MHz, C6D6, Si(CH3)4 = 0 ppm): δ(ppm) = 8.3558 (2H, d, 3 J = 3.65 Hz, 13,17-β-pyrroleH), 8.2820 (4H, brs, 2,8,12,18-β-pyrroleH), 8.2436 (2H, d, 3 J = 4.30 Hz, 3,7-β-pyrroleH), 8.0271 (2H, brs, 3,5-PyH), 6.5103 (2H, brs, 2,6-PyH), -3.6671 (2H, brs, inner pyrroleH). 19 19F NMR (470.34 MHz, CDCl3, CF3CO2H = -76.5 ppm): δ (ppm)= -128.3039 (2F, dd, 3 J F-F = 25.30 Hz, 5 J F-F = 12.84 Hz, 3,5-PhF Py ), -131.1393 (2F, dd, 3 J = 24.88 Hz, 5 J = 12.46 Hz, 2,6-PhF py ), -133.9887 (6F, dd, 3 JF-F = 23.21 Hz, 5 J F-F = 7.45 Hz, 2,6-PhF), -148.6199 (3F, m, 4-PhF), -158.7703 (4F, ddd, 3 J F-F = 21.34 Hz, 3 J F-F = 21.34 Hz, 5 J F-F = 6.62 Hz, 3.5-PhF). 13 C NMR(125.72 MHz, CDCl3, CDCl3= 77.0 ppm): δ (ppm)= 150.2754 (2,6-PyC), 148.2307-148.0316, 146.2278-146.0514 (2,6-Ph Py C), 147.6048-147.4626, 145.6474-145.4843 (3,5-PhC, 3,5-Ph py C), 144.8349 (4-PyC), 143.5117-143.2576, 141.4709-141.1389 (4-Ph py C, 4-PhC), 138.7851-138.4456, 136.7158-136.4484 (2,6-PhC), 131.2666 (1-Ph py C, 1-PhC, α-pyrroleC), 121.8589 (3,5-PyC), 115.6700, 115.4614, 115.2641 (β-pyrroleC), 111.5010, 104.0129-103.7815 (mesoC). Purity ( 19 F qNMR, 3,5-bis(trifluoromethyl)benzoic Acid): 91.2 wt% (TFPP·H2O).

[0114] TFPP(S-4py) trans-2 1 H NMR (499.91 MHz, C6D6, Si(CH3)4= 0 ppm): δ(ppm) = 8.3543 (4H, d, 3J= 3.95 Hz, 3,7,13,17β-pyrroleH), 8.2451 (4H, d, 3 J= 3.80 Hz, 2,8,12,18-β-pyrroleH), 8.0090 (4H, d, 3 J= 5.00 Hz, 3,5-PyH), 6.4986 (4H, d, 3 J= 4.45 Hz, 2,6-PyH), -3.646 (2H, s, inner pyrroleH). 19 F NMR (470.34 MHz, CDCl3, CF3CO2H= -76.5 ppm): δ (ppm)= -128.6677 (2F, dd, 3 J F-F = 24.46 Hz, 5 J F-F = 12.04 Hz, 3,5-PhF Py ), -132.5419 (2F, dd, 3 J = 24.86 Hz, 5 J = 12.44 Hz, 2,6-PhF py ), -134.3816 (6F, dd, 3 J F-F = 22.81 Hz, 5 J F-F = 5.36 Hz, 2,6-PhF), -148.8858 (2F, t, 3 J F-F = 20.76 Hz, 4-PhF), -159.1068 (4F, ddd, 3 J F-F = 21.57 Hz, 3 J F-F = 21.57 Hz, 5 J F-F = 4.97 Hz, 3.5-PhF). 13 C NMR(125.72 MHz, CDCl3, CDCl3= 77.0 ppm): δ (ppm)= 150.2905 (2,6-PyC), 148.2174-148.1036, 146.2145-146.1064 (2,6-Ph PyC), 147.6010-147.4872, 145.6000-145.4786 (3,5-PhC, 3,5-Ph py C), 144.8261 (4-PyC), 143.4974-143.2500, 141.4879-141.1731 (4-Ph py C, 4-PhC), 138.9293-138.4475, 136.7538-136.4370 (2,6-PhC), 131.2533 (1-Ph py C, 1-PhC, α-pyrroleC), 123.3004, 123.1449, 121.9932, 121.7546 (3,5-PyC), 115.6074-115.3324 (β-pyrroleC), 111.7135-111.3891, 104.0717, 103.8782 (mesoC).

[0115] TFPP(S-4py) cis-2 1 H NMR (499.91 MHz, CDCl3, Si(CH3)4= 0 ppm): δ(ppm) = 8.9878-8.9300 (8H, m, β-pyrroleH), 8.6609 (4H, brs, 3,5-PyH), 7.3668 (4H, d, 3 J= 5.00 Hz, 2,6-PyH), -2.8512 (2H, s, inner pyrroleH). 1 H NMR (499.91 MHz, C6D6, Si(CH3)4= 8.3420 (H, d, 3 J= 4.80 Hz, 3,12-β-pyrroleH), 8.2909 (2H, s, 7,8-β-pyrroleH), 8.2619 (2H, s, 17,18-β-pyrroleH), 8.2262 (2H, d, 3 J= 4.80 Hz, 2,13-β-pyrroleH), 8.0010 (4H, d, 3 J= 5.85 Hz, 3,5-PyH), 6.4841 (4H, d, 3J= 6.05 Hz, 2,6-PyH), -3.6741 (2H, s, inner pyrroleH). 19 F NMR (470.34 MHz, CDCl3, CF3CO2H= -76.5 ppm): δ (ppm)= -128.6933 (4F, dd, 3 J F-F = 24.88 Hz, 5 J F-F = 12.42 Hz, 3,5-PhF Py ), -132.5754 (4F, dd, 3 J = 24.90 Hz, 5 J = 12.44 Hz, 2,6-PhF py ), -134.4160 (4F, dd, 3 J F-F = 23.66 Hz, 5 J F-F = 7.06 Hz, 2,6-PhF), -148.9599 (2F, t, 3 J F-F = 20.72 Hz, 4-PhF), -159.1517 (4F, ddd, 3 J F-F = 21.78 Hz, 3 J F-F = 21.78 Hz, 5 J F-F = 7.20 Hz, 3.5-PhF). 13 C NMR(125.72 MHz, CDCl3, CDCl3= 77.0 ppm): δ (ppm)= 150.2905 (2,6-PyC), 148.2269-148.1359, 146.2278-146.1387 (2,6-Ph Py C), 147.5745-147.5327, 145.6057 (3,5-PhC, 3,5-Ph py C), 144.8242-144.7711 (4-PyC), 143.4966-143.3884, 141.4007-141.3419 (4-Ph pyC, 4-PhC), 138.7093-138.6581, 136.7386-136.6248 (2,6-PhC), 131.4373 (1-PhC) py C, 1-PhC, α-pyrroleC), 123.3004-123.0159, 121.8381-121.7584 (3,5-PyC), 115.6378-115.3589 (β-pyrroleC), 111.7476-111.4233, 104.1437-103.9332 (mesoC).

[0116] [Compound Synthesis 35] Synthesis of 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorin (TFPC(S-4Py)4)

[0117] Using the synthesis method for TFPP(S-4Py)1, 5,10,15,20-tetrakis(pentafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorin (TFPC, 160.0 mg, 155.1 μmol), 4-mercaptopyridine (270.9 mg, 637.8 μmol), and diisopropylamine (90 μL, 637.7 μmol) were reacted in a 200 mL solution, followed by partitioning with AcOEt / water. After evaporation of the organic layer, the crude product was purified by silica gel column chromatography (silica, φ = 63-210 μm, eluent; gradient from AcOEt:acetone:MeOH = 5:1:0 to 5:1:0.7 (v / v / v)). After evaporation of the solvent, TFPC(S-4Py)4 was obtained as a dark green powder in 57.2% yield.

[0118] [ka]

[0119] TFPC(S-4Py)4 1H NMR (499.91 MHz, acetone-d6, CD3C(=O)CD2H = 2.04 ppm): δ (ppm) = 9.2824 (2H, brs, 17,18-β-pyrroleH), 9.9649 (2H, brs, 2,13-β-pyrroleH), 8.9080 (2H, brs, 3,12-β-pyrroleH), 8.5752 (8H, brs, 3,5-PyH), 7.6290 (8H, m, 2,6-PyH), 5.5233 (2H, brs, 2,3-β-pyrroleH), 4.2728 (2H, brs, N-CHH), 3.2939 (2H, brs, N-CHH), 2.1300 (3H, s, N-CH3), -1.6719 (2H, brs, inner pyrroleH). 19 F NMR (470.34 MHz, acetone-d6, CF3CO2H= -76.5 ppm): δ (ppm)= -144.410(2F, m, 2,6-PhF Py ), -140.768 (2F, m, 2,6-PhF Py ), -141.892 (4F, m, 2,6-PhF Py ), -144.478 (2F, m, 3,5-PhF Py ), -146.518 (2F, m, 3,5-PhF Py ), -146.634 (4F, m, 3,5-PhF Py ).

[0120] [Synthesis of Compounds 14 and 15] Synthesis of 5,10,15-tris(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-20-(pentafluorophenyl)porphyrin (TFPP(S-4py)3) and 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)porphyrin (TFPP(S-4py)4) TFPP(S-4Py) 1-2The reaction mixture was prepared by the synthesis of 5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrin (TFPP, 600 mg, 616 μmol), 4-mercaptopyridine (240 mg, 2156 μmol), and diisopropylamine (435 μL, 3073 μmol), followed by separation. After evaporation of the solvent, the crude product was separated into its respective substituted forms by silica gel column chromatography (silica, φ = 63-210 μm, eluent; gradient from CHCl:AcOEt:acetone:MeOH = 1:1:0:0 to 0:0:1:1 (v / v / v / v)). Each substituted form was then purified by flash silica gel column chromatography (silica, φ = 40-50 μm, eluent; AcOEt:acetone:MeOH = 1:1:0:0 to 0:0:1:1 (v / v / v / v)). After evaporation of the solvent, TFPP(S-4Py)3 and TFPP(S-4Py)4 were obtained as reddish-brown powders in yields of 35.1% and 12.8%, respectively. TFPP(S-4py)3

[0121] [ka]

[0122] 1 H NMR (499.91 MHz, DMSO-d6, H-DMSO = 2.49 ppm): δ(ppm) = 8.7207-8.5912 (8H, m, β-pyrroleH), 7.7544 (6H, brs, 3,5-PyH), 6.8476 (6H, brs, 2,6-PyH), -4.0077 (2H, s, inner pyrroleH). 19 F NMR (470.34 MHz, DMSO-d6, CF3CO2H= -76.5 ppm): δ (ppm)= -141.2419 (6F, dd, 3 J F-F = 25.70 Hz, 5 J F-F= 10.79 Hz, 3,5-PhF Py ), -146.1985 (6F, dd, 3 J = 26.95 Hz, 5 J = 12.04 Hz, 2,6-PhF py ), -148.0046 (2F, m, 2,6-PhF), -162.3076 (1F, t, 3 J F-F = 22.39 Hz, 4-PhF), -171.2124 (2F, m, 3.5-PhF). 13 C NMR(125.72 MHz, DMSO-d6, C2D6OS= 39.5 ppm): δ (ppm)= 150.1474-150.0925 (2,6-PyC), 148.2545-148.2356, 146.2934-146.1265 (2,6-Ph Py C), 147.3897-147.2038, 145.4342-145.2255 (3,5-PhC, 3,5-Ph py C), 144.6641 (4-PyC), 142.9533, 141.0035 (4-Ph py C, 4-PhC), 138.5549, 136.5804 (2,6-PhC), 132.8553(1-Ph py C, 1-PhC, α-pyrroleC), 122.1352-121.7805, 1121.1242 (3,5-PyC), 114.5520 (β-pyrroleC), 110.0963-109.7630, 103.9269-103.4205 (mesoC).

[0123] TFPP(S-4py)4 1 H NMR (499.91 MHz, DMSO-d6, H-DMSO = 2.49 ppm): δ(ppm) = 8.7300 (8H, brs, β-pyrroleH), 7.7787 (8H, brs, 3,5-PyH), 6.8645 (8H, brs, 2,6-PyH), -3.9784 (2H, brs, inner pyrroleH).19 F NMR (470.34 MHz, DMSO-d6, CF3CO2H= -76.5 ppm): δ (ppm)= -141.2145 (8F, dd, 3 J F-F = 26.13 Hz, 5 J F-F = 9.52 Hz, 3,5-PhF Py ), -146.1703 (8F, dd, 3 J = 26.13 Hz, 5 J = 9.52 Hz, 2,6-PhF py ). 13 C NMR(125.72 MHz, DMSO-d6, C2D6OS= 39.5 ppm): δ (ppm)= 150.0830 (2,6-PyC), 148.2413-148.1218, 146.2782-146.1625 (2,6-Ph Py C), 147.3555-147.2398, 145.4000-145.2805 (3,5-Ph py C), 144.6698 (4-PyC, 4-Ph py C), 132.8743 (1-Ph py C, α-pyrroleC), 122.1162-121.8052, 121.1736 (3,5-PyC), 110.1196-109.7839 (β-pyrroleC), 103.9629 (mesoC).

[0124] [Compound Synthesis 16] Synthesis of 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(S-4py)1)

[0125] 5-4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(S-4py)1, 34.0 mg, 31.9 μmol) and zinc acetate dihydrate (21.1 mg, 96.1 μmol) were incubated in a MeOH (15 mL) / toluene (20 mL) mixed solvent for 4 hours at 120 o The mixture was heated to reflux at 10°C. The reaction mixture was dissolved in CHCl / AcOEt (10:1, v / v, ca. 100 mL) and separated with saturated brine (ca. 100 mL × 3). After distilling off the solvent, the crude product was separated by silica gel column chromatography (silica, φ = 63-210 μm, eluent; CHCl) to obtain the desired fraction solution. After distilling off the solvent, the residue was purified by flash silica gel column chromatography (silica, φ = 40-50 μm, eluent; CHCl), and the solvent was distilled off to obtain a red powder in 27.4% yield.

[0126] [ka]

[0127] 1 H NMR (499.91 MHz, CDCl3, Si(CH3)4= 0 ppm): δ(ppm) = 8.5165 (8H, m, β-pyrroleH), 8.3988 (2H, brs, 3,5-PyH), 8.2974 (2H, d, 2,6-PyH). 19 F NMR (470.34 MHz, acetone-d6, CF3CO2H= -76.5 ppm): δ (ppm)= -142.6529 (2F, dd, 3 J F-F = 23.61 Hz, 5 J F-F = 9.55 Hz, 3,5-PhF Py ), -146.1207 (2F, dd, 3 J = 25.28 Hz, 5J = 11.17 Hz, 2,6-PhF py ), -148.0917 (6F, dd, 3 J F-F = 23.63 Hz, 5 J F-F = 4.54 Hz, 2,6-PhF), -164.3472 (3F, t, 3 J F-F = 20.32 Hz, 4-PhF), -173.2678 (6F, m, 3.5-PhF). 13 C NMR(125.72 MHz, acetone-d6, CD3COCD3= 29.84 ppm): δ (ppm)= 150.7506 (2,6-PyC), 148.7628-148.4973, 146.7713-146.5778 (2,6-Ph Py C), 148.72981-148.1180, 146.3294-146.1454 (3,5-PhC, 3,5-Ph Py C), 144.1046 (4-PyC), 142.2306-141.9992 (4-Ph py C, 4-PhC), 137.9261-139.6321, 137.9346-137.6387 (2,6-PhC), 133.3939-133.2649 (1Ph py C, 1-PhC), 132.9823 (α-pyrroleC), 125.2324, 120.9952 (3,5-PyC), 117.7993-117.4920 (β-pyrroleC), 109.3552, 104.8600-104.5983 (mesoC).

[0128] [Synthesis of Compound 17] 5,15-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(S-4py) trans-2 Synthesis of (1) TFPP(S-4Py) 1-2Using the synthesis method described in [1], 5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrinate zinc(II) (Zn-TFPP, 274 mg, 264 μmol), 4-mercaptopyridine (62 mg, 554 μmol), and diisopropylamine (435 μL, 3073 μmol) were reacted and then separated. After distillation, the crude product was purified by silica gel column chromatography (silica, φ = 63-210 μm, eluent; CHCl:MeOH = 95:5 to 8:2 (v / v / v)) to separate the desired disubstituted product. After the solvent was evaporated, the residue was purified by flash silica gel column chromatography (silica, φ=40-50 μm, eluent; CHCl:MeOH:acetone=95:2.5:5 (v / v / v)), and the solvent was evaporated to give a pink powder.

[0129] [ka]

[0130] 1 H NMR (499.91 MHz, C6D6, Si(CH3)4= 0 ppm): δ(ppm) = 8.9830 (8H, brs, β-pyrroleH), 8.9649 (2H, d, 3 J = 4.25 Hz, 3,5-PyH), 8.8260 (2H, d, 3 J = 7.00 Hz, 2,6-PyH). 19 F NMR (470.34 MHz, CDCl3, Si(CH3)4= 0 ppm): δ(ppm) = -129.5598 ~ -129.6356 (4F, m, 2,6-PhF), -132.7578 ~ -132.8019 (2F, m, 3,5-PhF py ), -134.9810 ~ -135.0321 (2F, m, 2,6-PhF py ), -150.0653 (2F, t, 3 J F-F= 20.72 Hz, 4-PhF), -160.0280 ~ -160.1637 (2F, m, 3.5-PhF).

[0131] [Synthesis of Compound 17] 5,15-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(S-4py) trans-2 Synthesis of (2) Furthermore, Zn-TFPP(S-4py) was synthesized by a different synthesis method. trans-2 5,15-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrin (TFPP(S-4py)) was synthesized by referring to the synthesis of 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(S-4py)) described in the above Compound Synthesis 16 section. trans-2 After reacting the product with zinc acetate dihydrate (292.4 mg, 421.0 μmol), the mixture was separated into AcOEt and water. After distilling off the organic layer, the crude product was purified by silica gel column chromatography (silica, φ=63-210 μm, eluent; AcOEt) to obtain a red powder in a yield of 48.8%.

[0132] [ka]

[0133] [Compound Synthesis 36] 5,10-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(S-4py) cis-2 ) synthesis Using the synthesis of 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(S-4py)1) described in the synthesis of the above compound 16, 5,10-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrin (TFPP(S-4py) cis-2 After reacting the product with zinc acetate dihydrate (223.4 mg, 193.1 μmol), the mixture was separated into AcOEt and water. After distilling off the organic layer, the crude product was purified by silica gel column chromatography (silica, φ=63-210 μm, eluent; AcOEt) to obtain a red powder in 72.2% yield.

[0134] 1 H NMR (499.91 MHz, acetone-d6, CD3C(=O)CD2H = 2.04 ppm): δ(ppm) = 9.3238 (2H, brs, 3,12-β-pyrroleH), 9.2711 (2H, brs, 7,8-β-pyrroleH), 9.2578 (2H, brs, 17,18-β-pyrroleH), 9.1799 (2H, brs, 2,13-β-pyrroleH), 6.8547 (4H, brs, 3,5-PyH), 5.6990 (4H, brs, 2,6-PyH). 19 F NMR (470.34 MHz, acetone-d6, CF3CO2H= -76.5 ppm): δ (ppm)= -142.340 (4F, m, 2,6-PhF Py ), -146.180 (4F, dd, 3 J = 24.46 Hz, 5 J = 11.29 Hz, 3,5-PhF py ), -148.096 (4F, dd, 3J= 23.75 Hz, 5J= 5.41 Hz, 3,5-PhF), -164.319 (2F, t, 3J = 19.99 Hz, 4-PhF), -173.2075 (4F, m, 2,6-PhF).

[0135] [Synthesis of Compound 37] Synthesis of 5,10,15-tris(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-20-(pentafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(S-4py)3) Following the synthesis of 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(S-4py)1) described in the above Compound Synthesis 16 section, 5,10,15-tris(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-20-(pentafluorophenyl)porphyrin (TFPP(S-4py)3, 525.5 mg, 417.1 μmol) was reacted with zinc acetate dihydrate (976.8 mg, 4449.9 μmol), followed by separation with AcOEt / water. After distilling off the organic layer, the crude product was purified by silica gel column chromatography (silica, φ=63-210 μm, eluent; AcOEt : (acetone)) to obtain a red powder in a yield of 67.0%.

[0136] 1 H NMR (499.91 MHz, acetone-d6, CD3C(=O)CD2H = 2.04 ppm): δ(ppm) = 9.3071 (2H, brs, 2.18-β-pyrroleH), 9.2702 (6H, brs, 3,7,8,12,13,17-β-pyrroleH), 7.1422 (6H, brs, 3,5-PyH), 6.7415 (6H, brs, 2,6-PyH). 19F NMR (470.34 MHz, acetone-d6, CF3CO2H= -76.5 ppm): δ (ppm)= -142.270 (6F, m, 2,6-PhF Py ), -146.142 (6F, dd, 3 J = 25.40 Hz, 5 J = 11.29 Hz, 3,5-PhF py ), -148.078 (2F, m, 3,5-PhF), -164.132 (1F, m, 4-PhF), -173.112 (2F, m, 2,6-PhF).

[0137] [Compound Synthesis 18] Synthesis of 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)porphyrinate zinc(II) (Zn-TFPP(S-4py)4) Using the synthesis method for Zn-TFPP(S-4Py), 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)porphyrin (TFPP(S-4Py)4, 741 mg, 553 μmol) was reacted with zinc acetate dihydrate (585 mg, 2663 μmol) for 4 h, followed by separation. After evaporation of the solvent, the crude product was purified by silica gel column chromatography (silica, φ = 63-210 μm, eluent; gradient from CHCl:AcOEt:acetone:MeOH = 1:1:0:0 to 0:0:1:1 (d / v / v / v)). After evaporation of the solvent, a red powder was obtained in 82.1% yield.

[0138] [ka]

[0139] 1 H NMR (499.91 MHz, DMSO-d6, H-DMSO = 2.49 ppm): δ(ppm) = 8.5634 (8H, brs, β-pyrroleH), 7.7781 (2H, brs, 3,5-PyH), 6.8643 (2H, brs, 2,6-PyH). 1 H NMR (499.91 MHz, CDCl3 / CD3OD (= 5 / 1, v / v), Si(CH3)4= 0 ppm): δ(ppm) = 8.0382 (8H, brs, β-pyrroleH), 8.4030 (2H, brs, 3,5-PyH), 7.3858 (2H, brs, 2,6-PyH). 19 F NMR (470.34 MHz, DMSO-d6, CF3CO2H= -76.5 ppm): δ (ppm)= -141.2428 (8F, dd, 3 J F-F = 26.53 Hz, 5 J F-F = 10.77 Hz, 3,5-PhF Py ), -146.2046 (8F, dd, 3 J = 25.28 Hz, 5 J = 11.22 Hz, 2,6-PhF py ). 19 F NMR (470.34 MHz, CDCl3 / CD3OD (= 5 / 1, v / v), CF3CO2H= -76.5 ppm): δ (ppm)= -142.0035 ~ -142.0793 (2F, m, 3,5-PhF Py ), -145.9843 ~ -146.0654 (2F, m, 2,6-PhF py ).

[0140] [Synthesis of Compounds 19, 20, 21] 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4py)1), 5,15-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4py)trans-2 ), 5,10-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4py) cis-2 ) synthesis TFPP(S-4Py) 1-2 5,10,15,20-Tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP, 451 mg, 437 μmol), 4-mercaptopyridine (98 mg, 884 μmol), and diisopropylamine (150 μL, 1060 μmol) were reacted using the synthesis method described above, and the mixture was then separated. After evaporation of the solvent, the crude product was separated by silica gel column chromatography (silica, φ = 63-210 μm, eluent; gradient from CHCl:MeOH:acetone = 1:0:0 to 95:2.5:5 (v / v / v)). After evaporation of the solvent, each substituted compound was purified by flash silica gel column chromatography (silica, φ = 40-50 μm, eluent; gradient from CHCl:MeOH:acetone = 1:0:0 to 95:2.5:5 (v / v / v)). After evaporation of the solvent, the powder was washed with hexane to obtain reddish-brown Ni-TFPP(S-4Py)1 and Ni-TFPP(S-4Py). trans-2 and Ni-TFPP(S-4Py) cis-2 were obtained in yields of 55.5%, 2.8% and 6.4%.

[0141] [ka]

[0142] Ni-TFPP(S-4Py)1 1H NMR (499.91 MHz, CDCl3, Si(CH3)4= 0 ppm): δ(ppm) = 8.8824 (2H, brs, 3,7-β-pyrroleH), 8.8523 (6H, brs, 2,8,12,13,17,18-β-pyrroleH), 7.3686 (2H, brs, 3,5-PyH), 7.3686 (2H, brs, 2,4-PyH). 19 F NMR (470.34 MHz, CDCl3, CF3CO2H= -76.5 ppm): δ (ppm)= -128.5099 (2F, dd, 3 J F-F = 24.88 Hz, 5 J F-F = 12.46 Hz, 3,5-PhF Py ), -132.6036 (2F, dd, 3 J = 24.86 Hz, 5 J = 12.44 Hz, 2,6-PhF py , -134.4407 (6F, dd, 3 J F-F = 23.23 Hz, 5 J F-F = 7.48 Hz, 2,6-PhF), -149.0657 (3F, t, 3 J F-F = 22.92 Hz, 4-PhF), -158.9702 (6F, ddd, 3 J F-F = 18.45 Hz, 3 J F-F = 18.45 Hz, 5 J F-F = 5.82 Hz, 3.5-PhF). 13 C NMR (125.72 MHz, CDCl3, CDCl3= 77.0 ppm): δ (ppm)= 149.8391 (3,5-PyC), 147.271-147.2217, 145.3136-145.2131 (4-Ph Py C, 4-PhC), 144.5378 (3,5-Ph PyC), 143.8778-143.2348, 141.4538-141.2565 (3,5-PhC), 138.6922-138.6239, 136.5812 (2,6-PhC), 133.7361-33.4668 (1-Ph Py C), 133.5844 (1-PyC), 128.8066 (1-PhC), 122.6025 (α-pyrroleC), 114.5016-111.3569 (β-pyrroleC), 111.4536-111.3569 (2,6-PyC), 103.54440, 103.33950 (mesoC).

[0143] Ni-TFPP(S-4Py) trans-2 1 H NMR (499.91 MHz, CDCl3, Si(CH3)4= 0 ppm): δ(ppm) = 8.8324 (8H, m, β-pyrroleH), 8.6379 (4H, d, 3 J= 5.20 Hz, 3,5-PyH), 7.3213 (4H, d, 3 J= 5.15 Hz, 2,4-PyH). 19 F NMR (470.34 MHz, DMSO-d6, CF3CO2H= -76.5 ppm): δ (ppm)= -141.23481- -141.3353 (2F, m, 3,5-PhF Py ), -145.8521- -145.9772 (2F, m, 2,6-PhF py ), -147.6573- -147.7702 (6F, m, 2,6-PhF), -162.4205- -162.5051 (4F, m, 4-PhF), -171.1736- -171.2900 (6F, m, 3.5-PhF).

[0144] Ni-TFPP(S-4Py) cis-2 1H NMR (499.91 MHz, C6D6, Si(CH3)4= 0 ppm): δ(ppm) = 8.98183 (8H, brs, β-pyrroleH), 8.84251 (4H, brs, 3,5-PyH), 7.38196 (4H, brs, 2,4-PyH). 19 F NMR (470.34 MHz, CDCl3, CF3CO2H= -76.5 ppm): δ (ppm)= -128.5350 (4F, dd, 3 J F-F = 21.99 Hz, 5 J F-F = 10.37 Hz, 3,5-PhF Py ), -132.667 (4F, dd, 3 J = 21.96 Hz, 5 J = 10.35 Hz, 2,6-PhF py ), -134.4980 (4F, dd, 3 J F-F = 25.28 Hz, 5 J F-F = 6.23 Hz, 2,6-PhF), -149.0140 (2F, t, 3 J F-F = 19.8464 Hz, 4-PhF), -158.9790 (4F, m, 3.5-PhF). 13 C NMR (125.72 MHz, CDCl3 / CD3OD (= 5:1, v / v), CDCl3= 77.0 ppm): δ (ppm)= 149.14840 (3,5-PyC), 147.8530-147.0336, 146.0473-146.0322 (4-Ph Py C), 145.8785-145.0724 (4-PhC), 144.1639-144.0824 (3,5-Ph Py C), 143.6082-143.4963, 142.5593 (3,5-PhC), 138.5459-138.2842, 136.5847-136.2775 (2,6-PhC), 133.9085-133.7909 (1-Ph PyC, 1-PyC), 122.1546-122.0959 (1-PhC), 121.9877 (α-pyrroleC), 114.1089 (β-pyrroleC), 110.8484 (2,6-PyC), 103.4343, 103.3186 (mesoC).

[0145] [Synthesis of Compounds 22, 23] Synthesis of 5,10,15-tris(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-20-pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4py)3) and 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4py)4) TFPP(S-4Py) 1-2 5,10,15,20-Tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP, 906 mg, 878 μmol), 4-mercaptopyridine (442 mg, 3972 μmol), and diisopropylamine (585 μL, 4134 μmol) were reacted using the synthesis method described above, followed by separation. After evaporation of the solvent, the crude product was purified by silica gel column chromatography (silica, φ = 63-210 μm, eluent; gradient from CHCl:AcOEt:acetone:MeOH = 1:1:0:0 to 0:0:1:1 (v / v / v / v)). The residue was purified by flash silica gel column chromatography (silica, φ = 40-50 μm, eluent; acetone:MeOH = 1:2 (v / v)). After evaporation of the solvent, the reddish-brown Ni-TFPP(S-4Py)3 and Ni-TFPP(S-4Py)4 were obtained in yields of 12.9% and 72.7%, respectively. The yield was 72.7%.

[0146] [ka]

[0147] Ni-TFPP(S-4Py)3 1 H NMR (499.91 MHz, CDCl3 / CD3OD (= 5 / 1, v / v), Si(CH3)4= 0 ppm): δ(ppm) = 9.0316 ~ 8.9873(6H, m, β-pyrroleH), 8.6016 (2H, brs, 3,5-PyH), 7.4335 (2H, brs, 2,4-PyH). 19 F NMR (470.34 MHz, CDCl3 / CD3OD (= 5 / 1, v / v), Si(CH3)4= -76.5 ppm): δ(ppm)= -128.4691 (6F, dd, 3 J F-F = 24.06 Hz, 5 J F-F = 10.79 Hz, 3,5-PhF Py ), -132.5521 (6F, dd, 3 J F-F = 24.46 Hz, 5 J F-F = 12.04 Hz, 2,6-PhF py ), -134.6210 (1F, dd, 3 J F-F = 2.89 Hz, 5 J F-F = 6.23 Hz, 2,6-PhF), -142.0089 (1F, dd, 3 J F-F = 2.92 Hz, 5 J F-F = 4.56 Hz, 2,6-PhF), -149.3067 (3F, m, 4-PhF), -159.2236 (2F, m, 3.5-PhF).

[0148] Ni-TFPP(S-4Py)4 1 H NMR (499.91 MHz, CDCl3 / CD3OD (= 5 / 1, v / v), Si(CH3)4= 0 ppm): δ(ppm) = 9.0319 (2H, brs, β-pyrroleH), 8.5809 (2H, brs, 3,5-PyH), 7.4316 (2H, brs, 2,4-PyH). 19 F NMR (470.34 MHz, DMSO-d6, CF3CO2H= -76.5 ppm): δ(ppm) = -128.4752 (6F, dd, 3 J F-F = 26.53 Hz, 5 J F-F = 10.82 Hz, 3,5-PhF Py ), -133.4390 (6F, dd, 3 J F-F = 26.55 Hz, 5 J F-F = 11.59 Hz, 2,6-PhF py ).

[0149] [Synthesis of Compound 24] 5-(4-(1-methyl-4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(S-4Py) + Synthesis of -Me)1) 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(S-4py)1, 52.1 mg, 48.9 μmol) and methyl iodide (10 μL, 160.6 μmol) were dissolved in DMF (20 mL) and incubated in the dark for 50 min. oThe reaction mixture was reacted at C for 4 hours. The reaction mixture was dissolved in CHCl / AcOEt (=1:1, v / v, ca. 100 mL) and separated with saturated saline (ca. 100 mL × 3). After evaporation of the solvent, the crude product was purified by silica gel column chromatography (silica, φ = 63-210 μm, eluent; CHCl:MeOH = 8:2 (v / v)). After evaporation of the solvent, the residue was purified by flash silica gel column chromatography (silica, φ = 40-50 μm, eluent; AcOEt:acetone:MeOH = 1:1 (v / v / v)). After evaporation of the solvent, reddish-brown TFPP (S-4Py-Me + )1 was obtained in a yield of 61.0%.

[0150] [ka]

[0151] 1 H NMR (499.91 MHz, CDCl3, Si(CH3)4= 0 ppm): δ(ppm) = 9.2192 (2H, m, β-pyrroleH), 8.9937 (2H, brs, 3,5-PyH), 8.9153 (6H, m, β-pyrroleH), 8.0550 (2H, brs, 2,6-PyH), 4.5983 (3H, brs, CH3), -2.9009 (2H, brs, inner pyrroleH). 19 F NMR (470.34 MHz, CDCl3, CF3CO2H= -76.5 ppm): δ(ppm) = -127.7589 (2F, dd, 3 J F-F = 22.81 Hz, 5 J F-F = 11.19 Hz, 3,5-PhF Py ), -129.9864 (2F, dd, 3 J = 22.81 Hz, 5 J = 10.39 Hz, 2,6-PhF py ), -134.3737 (6F, dddd,3 J F-F = 21.00 Hz, 3 J F-F = 19.58 Hz, 3 J F-F = 19.58 Hz, 5 J F-F = 7.25 Hz, 2,6-PhF), -149.0366 (3F, ddd, 3 J F-F = 20.73 Hz, 3 J F-F = 20.73 Hz, 5 J F-F = 13.81 Hz, 4-PhF), -159.1659 (6F, ddd, 3 J F-F = 21.54 Hz, 3 J F-F = 21.54 Hz, 5 J F-F = 6.07 Hz, 3.5-PhF).

[0152] [Synthesis of Compound 25] 5-(4-(1-methyl-4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate Nickel(II) (Ni-TFPP(S-4Py + Synthesis of -Me)1) TFPP(S-4Py +Using the synthesis method of 5-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate nickel(II) (Ni-TFPP(S-4py)1, 1210.6 mg, 107.3 μmol) and methyl iodide (20 μL, 321.3 μmol), the mixture was separated. After distilling off the solvent, the residue was purified by silica gel column chromatography (silica, φ= 63-210 μm, eluent; CHCl:MeOH = 8:2 (= v / v)) followed by flash silica gel column chromatography (silica, φ= 40-50 μm, eluent; CHCl:MeOH = 8:2 (= v / v)). After distilling off the solvent, the residue was washed with hexane to give red Ni-TFPP(S-4Py-Me + ) 1 was obtained in 84.3% yield.

[0153] [ka]

[0154] 1 H NMR (499.91 MHz, CDCl3, Si(CH3)4= 0 ppm): δ(ppm) = 9.2580 (2H, brs, 2,6-PyH), 9.0002, 8.8616, 8.7074 (8H, m, β-pyrroleH), 7.8809 (2H, brs, 3,5-PyH), 4.5643 (3H, brs, CH3). 19 F NMR (470.34 MHz, CDCl3, CF3CO2H= -76.5 ppm): δ(ppm) = -127.6390 (2F, dd, 3 J F-F = 21.57 Hz, 5 J F-F = 9.10 Hz, 3,5-PhF Py ), -130.4316 (2F, m, 2,6-PhF py), -134.6152 (6F, m, 2,6-PhF), -149.1379 (3F, t, 3 J F-F = 20.74 Hz, 4-PhF), -159.0663 (6F, m, 3.5-PhF).

[0155] [Synthesis of Compound 26] 5-(4-(polyethylene glycol 400)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(PEG 400 ) Synthesis of 1) 5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrin (TFPP, 107 mg, 110 μmol), PEG 400 (Polyethylene glycol with an average molecular weight of 400: 91 mg, 228 μmol) was dissolved in 10 mL of DMF. o While cooled at 100°C, 76 mg (677 μmol) of potassium tert-butoxide was added and stirred for 15 minutes. 30 mL of cold water was added to the reaction solution and stirred for 5 minutes, after which the solvent was distilled off. The residue was washed with hexane (containing a small amount of CHCl) and water, and then dried to obtain a reddish-brown TFPP(PEG 400 ) 1 was obtained. TFPP(PEG 400 ) 1 was determined to be [M + Na] by ESI mass spectrometry. + = 1409.5 Na adduct.

[0156] [ka]

[0157] [Synthesis of Compound 27] 5-(4-(polyethylene glycol 1000)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(PEG 1000 ) Synthesis of 1) TFPP(PEG 400) 1 was synthesized using the synthesis method of 5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrin (TFPP, 93.4 mg, 96 μmol), PEG 1000 (Polyethylene glycol with an average molecular weight of 1000: 204 mg, 204 μmol), potassium tert-butoxide 81 mg (801 μmol) -15 o After reacting for 15 minutes at room temperature, the mixture was reacted for 3 hours. After that, 30 mL of cold water was added, and the solvent was distilled off. The residue was washed with CHCl3, hexane, and a small amount of water, and then dried to obtain a reddish-brown TFPP(PEG 1000 ) 1 was obtained. TFPP(PEG 1000 ) 1 was determined to be [M + Na] by ESI mass spectrometry. + = 1962.1 as a Na adduct.

[0158] [ka]

[0159] [Synthesis of Compound 28] 5-(4-(polyethylene glycol 4000)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (TFPP(PEG 4000 ) Synthesis of 1) TFPP(PEG 400 ) 1 was synthesized using the synthesis method of 5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrin (TFPP, 90.8 mg, 93 μmol), PEG 4000 (Polyethylene glycol with an average molecular weight of 4000: 302 mg, 754 μmol), potassium tert-butoxide 102 mg (1007 μmol) -15 o After reacting for 30 minutes at room temperature, the mixture was reacted for 24 hours. After that, 30 mL of cold water was added, and the solvent was distilled off. The residue was washed with CHCl3, hexane, and a small amount of water, and then dried to obtain a reddish-brown TFPP(PEG 4000 ) 1 was obtained. TFPP(PEG 1000) 1 was determined to be [M + Na] by ESI mass spectrometry. + = 4590.8 as an Na adduct.

[0160] [ka]

[0161] [Preparation of porphyrin compounds supported on silica gel] The above porphyrin compound-supported silica gel was prepared by the following method.

[0162] [Preparation of Porphyrin Compound-Supported Silica Gel 1] Preparation of TFPP-Supported Silica Gel TFPP (50.6 mg, 25.6 μmol) was placed in a 200 mL eggplant-shaped flask and dissolved in CH2Cl2: hexane. After adding 50 mL of a 50% aqueous ethanol (8:2, v / v) to dissolve the TFPP, 125 mg of silica gel 60N (spherical, neutral, 63-210 μm, Kanto Chemical Co., Ltd.) was added, and the solvent was distilled off while slowly stirring at 60°C. After that, the sample prepared in the clean bench was placed in a sample tube, ethanol was added, and the tube was air-dried. After that, the tube was placed in a sterilized bag and stored for 60°C. o The silica gel was dried in a dryer at 37°C. As a result, a purple TFPP-supported silica gel was obtained, in which TFPP was quantitatively supported on the silica gel with a supported amount of 205 μmol / g of silica gel.

[0163] [Preparation of Porphyrin Compound-Supported Silica Gel 2] Preparation of TFPC-Supported Silica Gel TFPC (25.1 mg, 24.3 μmol) was placed in a 200 mL recovery flask and dissolved in CH2Cl2: hexane. After adding 50 mL of a 50% ethanol (8:2, v / v) mixture to dissolve TFPC, 130 mg of silica gel 60N (spherical, neutral, 63-210 μm, Kanto Chemical Co., Ltd.) was added and the mixture was stirred for 60 minutes. o The solvent was distilled off while slowly stirring at 200 C. After that, the sample prepared in the clean bench was placed in a sample tube, which was then placed in a sterilized bag and left for 60 oThe silica gel was dried in a dryer at 37°C. As a result, TFPC was quantitatively supported on the silica gel with a loading amount of 187 μmol / g of silica gel, and a green TFPC-supported silica gel was obtained.

[0164] [Preparation of Porphyrin Compound-Supported Silica Gel 3] TFPP(mEt) trans-2 Preparation of supported silica gel TFPP(mEt) in a 100 mL eggplant-shaped flask trans-2 (25.4 mg, 23.3 μmol) and 20 mL of CHCl: AcOEt (1:1, v / v) was added to prepare TFPP(mEt). trans-2 After dissolving the above, 5108 mg of silica gel (medium granules (white), 3-5 mm, Fujifilm Wako Co., Ltd.) was added and the mixture was stirred for 80 minutes. o The solvent was slowly distilled off at 121°C. After that, the sample prepared in the clean bench was placed in a sample tube, which was then placed in a sterilization bag and autoclaved (121°C). o C, 20 min), then sterilized at 60 o The sample was then dried in a dryer at 37°C. After that, the sample tube was fitted with a cap sterilized with ethanol in a clean bench. As a result, the loading amount was 4.56 μmol / g of silica gel, and TFPP(mEt) was quantitatively determined. trans-2 TFPP(mEt) is supported on silica gel and has a reddish-brown color. trans-2 A silica gel support was obtained.

[0165] [Preparation of Porphyrin Compound-Supported Silica Gel 4] TFPP(mEt) cis-2 Preparation of supported silica gel TFPP(mEt) in a 100 mL eggplant-shaped flask cis-2 (25.5 mg, 23.4 μmol) and 20 mL of CHCl: AcOEt (1:1, v / v) was added to prepare TFPP(mEt). cis-2 After dissolving the above, 5163 mg of silica gel (medium granules (white), 3-5 mm, Fujifilm Wako Co., Ltd.) was added and the mixture was stirred for 80 minutes. o The solvent was slowly distilled off at 121°C. After that, the sample prepared in the clean bench was placed in a sample tube, which was then placed in a sterilization bag and autoclaved (121°C). oC, 20 min), then sterilized at 60 o The sample was then dried in a dryer at 37°C. After that, the sample tube was fitted with a cap sterilized with ethanol in a clean bench. As a result, the loading amount was 4.53 μmol / g of silica gel, and TFPP(mEt) was quantitatively determined. cis-2 TFPP(mEt) is supported on silica gel and has a reddish-brown color. cis-2 Supported silica gel was obtained.

[0166] [Preparation of Porphyrin Compound-Supported Silica Gel 5] Preparation of TFPP(mEt)3-Supported Silica Gel TFPP(mEt)3 (25.0 mg, 21.8 μmol) was added to a 100 mL recovery flask in 20 mL of CHCl:AcOEt (1:1, v / v) to dissolve TFPP(mEt)3, and then 5027 mg of silica gel (medium granular (white), 3-5 mm, Fujifilm Wako Co., Ltd.) was added. o The solvent was slowly distilled off at 121°C. After that, the sample prepared in the clean bench was placed in a sample tube, which was then placed in a sterilization bag and autoclaved (121°C). o C, 20 min), then sterilized at 60 o The sample was then dried in a 300°C dryer. Then, a cap sterilized with ethanol was attached to the sample tube in a clean bench. As a result, TFPP(mEt)3 was quantitatively supported on the silica gel with a loading amount of 4.33 μmol / g of silica gel, yielding a reddish-brown TFPP(mEt)3-supported silica gel. A photograph of the surface of the resulting TFPP(mEt)3-supported silica gel is shown in Figure 1.

[0167] [Preparation of Porphyrin Compound-Supported Silica Gel 6] Preparation of TFPP(mEt)4-Supported Silica Gel TFPP(mEt)4 (25.6 mg, 21.2 μmol) was placed in a 100 mL eggplant-shaped flask, and 50 mL of CHCl:AcOEt (1:1, v / v) was added to dissolve TFPP(mEt)4. 25 mg of silica gel (medium granular (white), 3-5 mm, Fujifilm Wako Co., Ltd.) was then added, and the mixture was stirred for 80 minutes. oThe solvent was slowly distilled off at 121°C. After that, the sample prepared in the clean bench was placed in a sample tube, which was then placed in a sterilization bag and autoclaved (121°C). o C, 20 min), then sterilized at 60 o The sample was then dried in a dryer at 37°C. Then, a cap sterilized with ethanol was attached to the sample tube in a clean bench. As a result, TFPP(mEt)4 was quantitatively supported on the silica gel with a loading amount of 4.22 μmol / g of silica gel, and a reddish-brown TFPP(mEt)4-supported silica gel was obtained.

[0168] [Preparation of Porphyrin Compound-Supported Silica Gel 7] Preparation of Zn-TFPP(mEt)4-Supported Silica Gel Zn-TFPP(mEt)4 (21.1 mg, 16.6 μmol) was added to a 100 mL recovery flask in 20 mL of CHCl:AcOEt (1:1, v / v) to dissolve Zn-TFPP(mEt)4, and then 4003 mg of silica gel (medium granules (white), 3-5 mm, Fujifilm Wako Co., Ltd.) was added. o The solvent was slowly distilled off at 121°C. After that, the sample prepared in the clean bench was placed in a sample tube, which was then placed in a sterilization bag and autoclaved (121°C). o C, 20 min), then sterilized at 60 o The sample was then dried in a dryer at 37°C. Then, a cap sterilized with ethanol was attached to the sample tube in a clean bench. As a result, Zn-TFPP(mEt)4 was quantitatively supported on the silica gel at a loading amount of 4.15 μmol / g of silica gel, yielding a pink-colored silica gel supported with Zn-TFPP(mEt)4.

[0169] [Preparation of Porphyrin Compound-Supported Silica Gel 8] Preparation of Ni-TFPP(mEt)4-Supported Silica Gel Ni-TFPP(mEt)4 (153.9 mg, 121.8 μmol) was added to a 100 mL recovery flask in 80 mL of CHCl:acetone (1:1, v / v) to dissolve Ni-TFPP(mEt)4. After that, 150.2 g of silica gel (medium granular (white), 3-5 mm, Fujifilm Wako Co., Ltd.) was added and the mixture was stirred for 80 minutes. oThe solvent was slowly distilled off at 121°C. After that, the sample prepared in the clean bench was placed in a sample tube, which was then placed in a sterilization bag and autoclaved (121°C). o C, 20 min), then sterilized at 60 o The sample was dried in a dryer at 37°C. Then, a cap sterilized with ethanol was attached to the sample tube in a clean bench. As a result, a red Ni-TFPP(mEt)4-supported silica gel was obtained with a loading of 0.457 μmol / g of silica gel (loading rate: 56.4%).

[0170] [Preparation of Porphyrin Compound-Supported Silica Gel 9] Preparation of TFPP(S-4Py)3-Supported Silica Gel TFPP(S-4Py)3 (52.9 mg, 42.0 μmol) was added to a 100 mL eggplant-shaped flask in 35 mL of acetone:MeOH (1:1, v / v) to dissolve TFPP(S-4Py)3. After that, 40333 mg of silica gel (medium granules (white), 3-5 mm, Fujifilm Wako Co., Ltd.) was added and the mixture was stirred for 80 minutes. o The solvent was slowly distilled off at 121°C. After that, the sample prepared in the clean bench was placed in a sample tube, which was then placed in a sterilization bag and autoclaved (121°C). o C, 20 min), then sterilized at 60 o The sample was dried in a dryer at 37°C. Then, a cap sterilized with ethanol was attached to the sample tube in a clean bench. As a result, a reddish-brown TFPP(S-4Py)3-supported silica gel was obtained with a loading amount of 0.740 μmol / g of silica gel (loading rate: 63.1%).

[0171] [Preparation of Porphyrin Compound-Supported Silica Gel 10] Preparation of TFPP(S-4Py)4-Supported Silica Gel TFPP(S-4Py)4 (19.4 mg, 14.5 μmol) was added to a 100 mL recovery flask in 20 mL of acetone:MeOH (1:1, v / v) to dissolve TFPP(S-4Py)4. After that, 30008 mg of silica gel (medium granules (white), 3-5 mm, Fujifilm Wako Co., Ltd.) was added and the mixture was stirred for 80 minutes. oThe solvent was slowly distilled off at 121°C. After that, the sample prepared in the clean bench was placed in a sample tube, which was then placed in a sterilization bag and autoclaved (121°C). o C, 20 min), then sterilized at 60 o The sample was dried in a dryer at 37°C. Then, a cap sterilized with ethanol was attached to the sample tube in a clean bench. As a result, a reddish-brown TFPP(S-4Py)4-supported silica gel was obtained with a loading amount of 0.441 μmol / g of silica gel (loading rate: 91.2%).

[0172] [Preparation of Porphyrin Compound-Supported Silica Gel 11]Zn-TFPP(S-4Py) trans-2 Preparation of supported silica gel Using the preparation method of TFPP(S-4Py)4 supported silica gel, Zn-TFPP(S-4Py) trans-2 (14.7 mg, 12.1 μmol) and 25256 mg of silica gel (medium granules (white), 3-5 mm) to form pink Zn-TFPP(S-4Py) with a loading of 0.410 μmol / g of silica gel (loading rate: 85.7%). trans-2 A silica gel support was obtained.

[0173] [Preparation of Chlorin Compound-Supported Silica Gel] Preparation of TFPC(S-4Py)4-Supported Silica Gel Using the preparation method for TFPC(S-4Py)4-supported silica gel, a dark green TFPC(S-4Py)4-supported silica gel was obtained from TFPC(S-4Py)4 (19.4 mg, 13.9 μmol) and 30508 mg of silica gel (medium-sized white granules, 3-5 mm) with a loading of 0.311 μmol / g of silica gel (loading rate: 68.1%).

[0174] In the silica gel supports shown above, the loading rate on silica gel was almost quantitative (over 99%) for both the dye alone (TFPP or TFPC) and M-TFPP(mEt)4. The loading rate for Ni-TFPP(mEt)4 was low due to the large scale. Furthermore, the loading rate for TFPP(S-4Py)3, ​​which is highly water-soluble, was low at 63.1%, while the loading rate for TFPP(S-4Py)4 was 91.2%. Furthermore, the loading rate for Zn-TFPP(S-4Py) trans-2 The loading rates of TFPC(S-4Py)4 and TFPC(S-4Py)4 were 85.7% and 68.1%, respectively.

[0175] [Example 1] Photoinactivation test using Escherichia coli (E coli, W3110) In an L-shaped reaction tube equipped with a stirrer, a suspension of Escherichia coli (E. coli, W3110) in King's B (KB) solution (2 × 10 4 The cells / mL (10 mL) and 101 μL of 1 or 5 mmol porphyrin DMSO solution were added (final concentration: 1 μM or 5 μM in 1% DMSO / medium). The mixture was stirred in a dark place in a water bath at 30°C for 2 hours (light intensity: 0 J / cm). 2 ) LED DESK LAMP (DS-LS78-W, OHM ELECTRIC, Illuminance: 1.76 mW / cm 2 ), and simulated sunlight (UV / IR plant light 600W, GREENS IN DOOR, China, illuminance: 3.39 or 3.99 mW / cm 2 ) for 56.8 minutes, 29.5 minutes, or 25.1 minutes (light intensity: 6 J / cm 2 ), 114.0 minutes, 59.1 minutes or 50.1 minutes (light intensity: 12 J / cm 2 ), 100.2 min (24 J / cm 2 , Simulated sunlight illuminance: 3.99 mW / cm 2At each time point, a sample was taken from each reaction solution and the number of E. coli (cells / mL) was confirmed. The number of E. coli was confirmed by turbidity measurement (n = 4) and specific enzyme substrate culture method (n = 3). For turbidity measurement, the absorbance at 600 nm (4.29 × 10 7 × A 600 [cells mL -1 ], J. Photochem. Photobiol., 168 (2017) 124-131.), and for the specific enzyme substrate medium method, XM-G agar medium (Nissui Pharmaceutical Co.) was used, and the E. coli concentration was determined by each method. As a control, a sample cultured under 1% DMSO conditions was used as a vehicle, and commercial drugs such as hematoprofilin (HP: Fujifilm Wako Pure Chemical Industries, Ltd.) and glucose-linked profilin (Zn-TFPP(mEt)2(SGlc) trans-2 (S. Hirohara, et.al., In Spectroscopic Tools for the Diagnosis and Treatment of Cancer; Pacifichem Symposium Chapter (10), Sankeisha Co., Ltd., pp.94-103 (2018).) A similar test was conducted to examine the photosterilization (inactivation) ability of each porphyrin by comparing it with the E. coli concentration of porphyrin. trans-2 is expensive and the synthesis process is complicated, making it extremely difficult to use as an antibacterial agent. The results of the turbidity method and the specific enzyme substrate medium method were almost the same, so the results obtained by the turbidity method are shown in Tables 3 and 4 below (1 μM: 6, 12 J / cm 2 ), Tables 5 and 6 (5 μM: 6, 12, 24 J / cm 2 ) and Tables 5 and 6 are graphed in Figure 2.

[0176] [Table 3] Photoinactivation test of E. coli with porphyrin at a concentration of 1 μM using LED DESK LAMP (light dose: 6, 12 J / cm 2 )

[0177] [Table 4] Photoinactivation test of E. coli with porphyrin at a concentration of 1 μM using simulated sunlight (light dose: 6, 12 J / cm 2 )

[0178] [Table 5] Photoinactivation test of E. coli with porphyrin at a concentration of 5 μM using simulated sunlight (light dose: 6, 12, 24 J / cm 2 )

[0179] [Table 6] Photoinactivation test of E. coli with porphyrin at a concentration of 5 μM using simulated sunlight (light dose: 6, 12, 24 J / cm 2 )

[0180] The results in Tables 3, 4, 5, 6, and Figure 2 confirm that all porphyrin compounds have photobactericidal (inactivating) activity against E. coli. In addition, hematoprofin (HP) and Zn-TFPP(mEt)2(SGlc) trans-2 It was confirmed that it has a photosterilization (inactivation) effect compared to

[0181] [Example 2] Photosterilization (inactivation) test using Synechocystis sp. PCC 6803 To a test tube containing 50 mL of BG-11 medium (pH 7; see Rosmarie Rippka et al., J Gen Microbiol., 1979, 111:1-61), 2 g of porphyrin solution (final concentration 0.1-5 μM in 1% DMSO / medium) or porphyrin-loaded silica gel was added. Synechocystis sp. PCC 6803 (a model cyanobacterium) was added to the test tube so that the turbidity value (730 nm) reached 0.1. The tube was then incubated at 30°C under aeration and illuminated with fluorescent / LED light (200-300 μmol / m 2 / s, 24-hour continuous light irradiation). Samples were taken out daily, and turbidity measurements were taken to examine the photosterilization (inactivation) ability of porphyrin. Similar tests were also conducted with the following comparative substances: a moss inhibitor containing zeolite, alumina, etc. as active ingredients (commercial drug 1: Gex Best Co., Ltd.), a moss inhibitor containing higher fatty acid compounds as active ingredients (commercial drug 2: Kotobuki Kogei Co., Ltd.), a moss inhibitor containing metal-free natural ingredients as active ingredients (commercial drug 3: Beltec Japan Co., Ltd.), and 1% DMSO / medium as a vehicle. The amounts of the commercial drugs added were the amounts specified in their respective instructions.

[0182] Figure 3 shows the test results for (1) a system containing a commercially available drug solution, (2) a system containing TFPP(mEt)4 solution (final concentration: 1 μM in 1% DMSO / medium), (3) a system containing TFPP(mEt)4 and Zn-TFPP(mEt)4 solutions (final concentration: 50 or 10 μM in 1% DMSO / medium), (4) a system containing Zn-TFPP(mEt)4 solution (final concentration: 5 μM in 1% DMSO / medium), and (5) a system containing Zn-TFPP(mEt)4-loaded silica gel.

[0183] As is clear from the graphs in Figures 3(2) to (4), the use of TFPP(mEt)4 and Zn-TFPP(mEt)4 solutions inhibited the growth of Synechocystis sp. PCC 6803. In particular, the use of TFPP(mEt)4 solution at 10 μM completely inhibited the growth of Synechocystis sp. PCC 6803, and the use of Zn-TFPP(mEt)4 solution at 5 μM completely inhibited the growth of Synechocystis sp. PCC 6803, and this effect continued for 35 days. On the other hand, the use of commercially available drugs 1 and 2 caused growth of Synechocystis sp. PCC 6803 on the third day of culture, and the use of commercially available drug 3 on the tenth day of culture. The duration of the inhibitory effect on Synechocystis sp. PCC 6803 growth was less than 10 days.

[0184] Furthermore, as is clear from the graph in Figure 3(5), when Zn-TFPP(mEt)4 supported on silica gel was used, the growth of Synechocystis sp. PCC 6803 was inhibited by approximately half compared to the vehicle. Furthermore, when only the dyes (TFPP, TFPC) were bound, they were completely ineffective in a photobactericidal test using cyanobacteria. This was thought to be because the dyes were hydrophobic and did not dissolve in the solution even after sustained release.

[0185] Furthermore, the results of experiments using mercaptoethanol derivatives of Zn-TFPP(mEt)4 (Zn-PM4), H2-TFPC(mEt)4 (CM4), and Zn-TFPC(mEt)4 (Zn-CM4) solutions (final concentrations of 5 μM and 1 μM in 1% DMSO / medium, respectively), H2-TFPC(mEt)4-immobilized silica gel (CM4(Si)), Zn-TFPC(mEt)4-immobilized silica gel (Zn-CM4(Si)) (final concentrations of 0.5 μM in 1% DMSO / medium), and vehicle (1% DMSO / CM) are shown in Figure 4A. The numbers in parentheses after each agent refer to the horizontal axis of Figure 4A.

[0186] The results in Figure 4A show that even when the drug was added at a concentration of 0.5 µM, the drug supported on silica gel had a high growth inhibitory effect on Synechocystis sp. PCC 6803.

[0187] Figure 4B shows the results of experiments using porphyrin or chlorin solutions, and porphyrin- or chlorin-loaded silica gel solutions containing mercaptoethanol derivatives of Zn-TFPP(mEt)4 loaded silica gel (Zn-PM4(Si)), Zn-TFPC(mEt)4 loaded silica gel (Zn-CM4(Si)), TFPP(mEt)4(PM4), TFPC(mEt)4(CM4), Zn-TFPP(mEt)4(Zn-PM4), Zn-TFPC(mEt)4(Zn-CM4), TPPS, Zn-TFPP(mEt)2(Glc)2 (Zn-PM2G2) (final concentration 0.5 μM in 1% DMSO / medium), and vehicle (v) (1% DMSO / CM). The numbers in parentheses after each agent refer to the horizontal axis of Figure 4B.

[0188] Furthermore, pyrimidine compounds such as TFPP(S-4Py)4-supported silica gel (PPy4(Si)), TFPC(S-4Py)4-supported silica gel (CPy4(Si)), and Zn-TFPP(S-4Py) were used as porphyrin or chlorin solutions, and as porphyrin- or chlorin-supported silica gel solutions. trans-2 Supported silica gel (Zn-PPyt(Si)), TFPP(S-4Py)4(PPy4), Zn-TFPP(S-4Py)1(Zn-PPy1), Zn-TFPP(S-4Py) trans-2 (Zn-PPyt), Zn-TFPP(S-4Py) cis-2 (Zn-PPyc), Zn-TFPP(S-4Py)3(Zn-PPy3), Zn-TFPP(S-4Py)4(Zn-PPy4), TFPC(S-4Py)4(CPy4), TPPS, TFPP(S-4Py)1 +The results of the experiment using the system containing (PPy1+) (final concentration 0.5 μM in 1% DMSO / medium) and vehicle (v) (1% DMSO / CM) are shown in Figure 4C. The numbers in parentheses after each drug indicate the information on the horizontal axis of Figure 4C.

[0189] Figures 4B and 4C confirm that either the porphyrin or chlorin solution used had a high growth inhibitory effect on Synechocystis sp. PCC 6803, and that both drugs, when used as supports, exhibited long-term photoantibacterial activity. Note that the optimal concentration for each drug is different, and at the concentrations tested in this study, Zn-CM4(Si), CM4, Zn-ppyt(si), and PPy4 showed particularly strong antialgal effects.

[0190] [Example 3] Photosterilization (inactivation) test in a tank containing matsumo A tank containing water moss (Delta glabra) was filled with 21 cm of dechlorinated tap water (volume: 17.7 L) (length: width: height: 29 cm (inner diameter) × 29 cm (inner diameter) × 29 cm (inner diameter)) and 75 g of Zn-TFPP(mEt)4-loaded silica gel (dye loading: 394 nmol / g silica gel) was added. The water temperature in the tank was maintained at 25°C and 30°C with air circulation. The porphyrin's suppressive effect on water moss was investigated for one month under constant illumination from an LED light (LED Mini Eco Light (for 17-32 cm aquariums) Light Aquarium, Tetra) placed 19 cm above the water surface. For comparison, similar tests were conducted on a system containing soil (Project Soil: Aqua Systems Co., Ltd.), a system containing a moss inhibitor (commercial drug 2: Kotobuki Kogei Co., Ltd.) whose active ingredient is a higher fatty acid compound that showed high bactericidal effects in the above-mentioned test using Synechocystis sp. PCC 6803, a system containing 75 g of TFPP(mEt)4-loaded silica gel (dye loading: 397 nmol / 1 g silica gel), and a system containing 1% DMSO (vehicle). The amounts of the commercial drugs added were the amounts written in the instructions for each.

[0191] As a result, in the vehicle system, brown moss appeared one week after the test, followed by green moss, and one month later a foul odor was emitted from the tank.In the systems containing soil and the system containing commercially available moss suppressant drug 2, there was no foul odor from the tank even after one month of the test, but from around the 15th day of the test, beard moss began to appear around the aquatic plants, and one week later spotted algae appeared in the tank. On the other hand, in the system containing porphyrin-loaded silica gel, there was no odor, just like with soil, for one month of testing. However, green moss began to appear in the system containing TFPP(mEt)4-loaded silica gel from the 19th day of testing, and in the system containing Zn-TFPP(mEt)4-loaded silica gel from the 22nd day of testing. Furthermore, the Zn-TFPP(mEt)4-loaded silica gel showed less discoloration over time than the TFPP(mEt)4-loaded silica gel. Figure 5 shows the state of the aquarium after two weeks of testing in the system containing Zn-TFPP(mEt)4-loaded silica gel.

[0192] When Zn-TFPP(mEt)4-loaded silica gel was used, no odor was generated, and no green moss grew until the 21st day, with only a small amount growing even after the 22nd day.

[0193] [Example 4] Amount of active oxygen generated Using a solution of the synthesized porphyrin, singlet oxygen ( 1 The generation of hydroxyl radicals (·OH) and O2 was investigated.

[0194] Singlet oxygen ( 1 O2) Development test A DMSO solution of the synthesized porphyrin (c = 2.5 μM) / 1,3-diphenylisobenzofuran (DPBF, c = 399 μM) was prepared and placed in a rectangular fluorescence cell (1 cm). Oxygen gas was introduced into the solution for 1 minute before irradiation. The solution was then irradiated at 25°C with light from an optical fiber attached to a 150 W halogen lamp (KL1500 LCD, 3000 K: Schott Japan) through a Y-50 cutoff filter (λ > 500 nm, Toshiba). The concentration of DPBF was monitored by measuring the absorbance at 418 nm. The rate constant k' (s-1 ) was determined by a linear plot of DPBF concentration as a function of irradiation time. Tetraphenylsulfonic acid (TPPS) was used as a comparative substance, and the 1 The amount of O2 generated by each compound 1 O2 generation was standardized.

[0195] Hydroxy radical (·OH) generation test A 0.2% DMSO / PBS solution of the synthesized porphyrin (c = 0.2 μM) and hydroxyphenylfluorescein (HPF, c = 215 nM) was prepared and placed in a rectangular fluorescence cell (1 cm). Oxygen gas was introduced into the solution for 1 min before irradiation. The solution was then irradiated at 25°C with light from an optical fiber attached to a 150 W halogen lamp (KL1500 LCD, 3000 K: SCHOTT Japan) through a Y-50 cutoff filter (λ > 500 nm, Toshiba). The initial rate of increase in HPF fluorescence intensity was monitored by measuring the excitation and emission wavelengths at 485 and 535 nm. The rate constant was calculated from a linear plot of fluorescence intensity versus irradiation time. The amount of OH generated by each compound was normalized to that of hematoporphyrin (HP) as a reference material.

[0196] Singlet oxygen in porphyrin ( 1 Table 7 shows the relative amounts of O2 and hydroxyl radical (·OH) generated.

[0197] [Table 7]

[0198] (result) Table 7 shows that the introduction of metal ions and conversion to chlorin (TFPC) resulted in a higher amount of singlet oxygen generation than the free porphyrin (TFPP). With the exception of Zn-TFPP(S-4Py)4, which is poorly soluble in water, the zinc pyridine derivatives tended to generate more ·OH as the number of substitutions increased. It was also shown that the pyridine derivatives generated a higher amount of ·OH than the mercaptoethanol derivatives.

[0199] [Example 5] Photosterilization (inactivation) test in a pool In a swimming pool (WDH: 12.5 m × 25 m × 1.0–1.5 m, water volume: 375 tons) in Ube City, Yamaguchi Prefecture, approximately 55 g of TFPC(mEt)4-loaded silica gel (loading: 402.2 nmol / g silica gel) was placed on six floats and placed at four locations in the pool (replaced after two months). The test was conducted with aeration of the pool water for three hours per day using solar panels (Ube Koki Co., Ltd.). Bacterial counts in the pool water on day 72 were measured using a specific enzyme substrate culture method using XM-G agar medium and a water quality test kit (ammonia nitrogen, free residual chlorine, nitrate nitrogen, nitrite nitrogen, and phosphate ion), and water quality was confirmed visually. The results are shown in Figure 6.

[0200] As shown in Figure 6, even 72 days after the start of the test, there was no change in water quality, and no E. coli was detected, meaning bacterial growth was almost completely suppressed (bacterial count: 1.5 CFU / mL). In addition, in a typical chlorinated pool, the count is 100 CFU / mL or less (Ministry of Health, Labor and Welfare and WHO standards), while in a typical unchlorinated pool (or left unattended), the count is 1,000-10,000 CFU / mL or more. Therefore, in terms of bacterial count level, when TFPC(mEt)4-loaded silica gel was used, the results showed excellent photoantibacterial activity, suppressing bacterial counts to 1 / 67th of that of a typical pool (when chlorinated) and 1 / 6,700th of that of a typical pool (when not chlorinated).

Claims

1. General formula (I): 【Chemical 1】 (In the formula, M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si, or Al. X １ ~X ２０ are each independently, fluorine atoms, HOCH ２ CH ２ S-based, H (OCH ２ CH ２ ) ｎ O-group (n represents an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and X １ ~X ２０ At least one selected from HOCH ２ CH ２ S-based, H (OCH ２ CH ２ ) ｎ O-group (n represents an integer of 1 to 100), a 4-pyridinothio group, or It is a 1-methyl-4-pyridinothio group. A is a ring having a structure represented by the following formula (A1), a ring having a structure represented by formula (A2), a ring having a structure represented by formula (A3), a ring having a structure represented by formula (A4), or a ring having a structure represented by formula (A5), B is a ring having a structure represented by the following formula (B1), a ring having a structure represented by formula (B2), a ring having a structure represented by formula (B3), a ring having a structure represented by formula (B4), or a ring having a structure represented by formula (B5), C is a ring having a structure represented by the following formula (C1), a ring having a structure represented by formula (C2), a ring having a structure represented by formula (C3), a ring having a structure represented by formula (C4), or a ring having a structure represented by formula (C5): D is a ring having a structure represented by the following formula (D1), a ring having a structure represented by formula (D2), a ring having a structure represented by formula (D3), a ring having a structure represented by formula (D4), or a ring having a structure represented by formula (D5). wherein the wavy line indicates a binding site.) or a salt thereof as an active ingredient. 【Chemistry 2】

2. 2. The antibacterial or antialgal agent according to claim 1, wherein the compound represented by general formula (I) is a compound represented by the following formula (II) or formula (III): 【Chemistry 3】 wherein M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si, or Al; R １ ~R ４ are each independently a fluorine atom, HOCH ２ CH ２ S-group, H(OCH ２ CH ２ ) ｎ O- group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and R １ ~R ４ At least one selected from HOCH ２ CH ２ S-group, H(OCH ２ CH ２ ) ｎ O- group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group. 【Chemistry 4】 wherein M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si, or Al; R １ ~R ４ are each independently a fluorine atom, HOCH ２ CH ２ S-group, H(OCH ２ CH ２ ) ｎ O- group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and R １ ~R ４ At least one selected from HOCH ２ CH ２ S-group, H(OCH ２ CH ２ ) ｎ O- group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group.

3. 3. The antibacterial or antialgal agent according to claim 1, wherein M is two hydrogen atoms, Zn, Ni, Gd or Pd.

4. The R １ ~R ４ are the same group, and the same group is HOCH ２ CH ２ S-group, H(OCH ２ CH ２ ) ｎ 4. The antibacterial or antialgal agent according to claim 2 or 3, wherein the group is an O-group (n is an integer of 1 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group.

5. The compound represented by formula (I) (I-1) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate zinc(II), (I-2) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate nickel(II), (I-3) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate palladium(II), (I-4) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate gadolinium(III), (I-5) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorin, (I-6) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate palladium(II), (I-7) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate gadolinium(III), (I-8) 5,10,15,20-Tetrakis(4-(2-acetylethylthio)-2,3,5,6-tetrafluorophenyl)porphyrinate zinc(II) (I-9) 5,10,15,20-tetrakis(4-(2-acetylethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate zinc(II), (I-10) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorinate zinc(II), (I-11) 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin, (I-12) 5,15-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrin, (I-13) 5,10-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrin, (I-14) 5,10,15-tris(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-20-(pentafluorophenyl)porphyrin, (I-15) 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)porphyrin, (I-16) 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate zinc(II), (I-17) 5,15-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrinate zinc(II), (I-18) 5,10,15,20-tetrakis-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)porphyrinate zinc(II), (I-19) 5-(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate nickel(II), (I-20) 5,15-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrinate nickel(II), (I-21) 5,10-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrinate nickel(II), (I-22) 5,10,15-tris(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-20-(pentafluorophenyl)porphyrinate nickel(II), (I-23) 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)porphyrinate nickel(II), (I-24) 5-(4-(1-methyl-4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin, (I-25) 5-(4-(1-methyl-4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrinate nickel(II), (I-26) 5-(4-(polyethylene glycol 400)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin, (I-27) 5-(4-(polyethylene glycol 1000)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin, (I-28) 5-(4-(polyethylene glycol 4000)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (I-29) 5-(4-(2-hydroxyethoxy)-2,3,5,6-tetrafluorophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin, (I-30) 5,15-bis(4-(2-hydroxyethoxy)-2,3,5,6-tetrafluorophenyl)-10,20-bis(pentafluorophenyl)porphyrin, (I-31) 5,10-bis(4-(2-hydroxyethoxy)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrin, (I-32) 5,10,15-tris(4-(2-hydroxyethoxy)-2,3,5,6-tetrafluorophenyl)-20-(pentafluorophenyl)porphyrin, (I-33) 5,10,15,20-tetrakis(4-(2-hydroxyethoxy)-2,3,5,6-tetrafluorophenyl)porphyrin, (I-34) 5,10,15,20-tetrakis(4-(2-hydroxyethylthio)-2,3,5,6-tetrafluorophenyl)porphyrin, (I-35) 5,10,15,20-tetrakis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-2,3-(methano(N-methyl)-iminomethano)chlorin, (I-36) 5,10-bis(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-15,20-bis(pentafluorophenyl)porphyrinate zinc(II), or (I-37) 5,10,15-tris(4-(4-pyridinothio)-2,3,5,6-tetrafluorophenyl)-20-(pentafluorophenyl)porphyrinate zinc(II) 2. The antibacterial or antialgal agent according to claim 1, wherein

6. General formula (IV): 【Chemistry 5】 (In the formula, M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si, or Al. X １ ~X ２０ are each independently, Fluorine atom, H(OCH ２ CH ２ ) ｎ O- group (n is an integer of 2 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and X １ ~X ２０ At least one selected from H(OCH ２ CH ２ ) ｎ O-group (n is an integer of 2 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group. A is a ring having a structure represented by the following formula (A1), a ring having a structure represented by formula (A2), a ring having a structure represented by formula (A3), a ring having a structure represented by formula (A4), or a ring having a structure represented by formula (A5), B is a ring having a structure represented by the following formula (B1), a ring having a structure represented by formula (B2), a ring having a structure represented by formula (B3), a ring having a structure represented by formula (B4), or a ring having a structure represented by formula (B5), C is a ring having a structure represented by the following formula (C1), a ring having a structure represented by formula (C2), a ring having a structure represented by formula (C3), a ring having a structure represented by formula (C4), or a ring having a structure represented by formula (C5): D is a ring having a structure represented by the following formula (D1), a ring having a structure represented by formula (D2), a ring having a structure represented by formula (D3), a ring having a structure represented by formula (D4), or a ring having a structure represented by formula (D5). wherein the wavy line indicates a binding site.) or a salt thereof. 【Chemistry 6】

7. The compound or salt thereof according to claim 6, wherein the compound represented by general formula (IV) is a compound represented by the following formula (V) or formula (VI): 【Chemistry 7】 (Wherein, M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si or Al; R １ ~R ４ are each independently a fluorine atom, H(OCH ２ CH ２ ) ｎ O- group (n is an integer of 2 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and R １ ~R ４ At least one selected from H(OCH ２ CH ２ ) ｎ O- group (n is an integer of 2 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group. 【Chemistry 8】 (Wherein, M is two hydrogen atoms, Zn, Ni, Gd, Pd, Pt, Si or Al; R １ ~R ４ are each independently a fluorine atom, H(OCH ２ CH ２ ) ｎ O- group (n is an integer of 2 to 100), a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group, and R １ ~R ４ At least one selected from H(OCH ２ CH ２ ) ｎ O- group (n is an integer of 2 to 100), a 2-hydroxyethylthio group, a 4-pyridinothio group, or a 1-methyl-4-pyridinothio group.

8. 8. The compound or salt thereof according to claim 6, wherein M is two hydrogen atoms, Zn, Ni, Gd, or Pd.

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