Novel chlorin e6 analogues

Abstract

The present invention relates to chlorin e6 analogs and pharmaceutically acceptable salts thereof, and compositions comprising chlorin w6 analogs and pharmaceutically acceptable salts thereof. The chlorin e6 analogs and pharmaceutically acceptable salts thereof are suitable for use in photodynamic therapy, cytoluminescence therapy, and photodynamic diagnosis, for example, for the treatment or detection of tumors or antiviral treatment. The present invention also relates to the use of chlorin e6 analogs and pharmaceutically acceptable salts thereof in the manufacture of phototherapeutic or photodiagnostic agents, and to methods of photodynamic therapy, cytoluminescence therapy, or photodynamic diagnosis, for example, for the treatment or detection of tumors or antiviral treatment. [Formula 1] TIFF2025539865000117.tif70159

Description

[Technical Field]

[0001] The present invention relates to chlorin e6 analogs and pharmaceutically acceptable salts thereof, and compositions comprising chlorin w6 analogs and pharmaceutically acceptable salts thereof. The chlorin e6 analogs and pharmaceutically acceptable salts thereof are suitable for use in photodynamic therapy, cytoluminescence therapy, and photodynamic diagnosis, for example, for the treatment or detection of tumors or antiviral treatment. The present invention also relates to the use of chlorin e6 analogs and pharmaceutically acceptable salts thereof in the manufacture of phototherapeutic or photodiagnostic agents, and to methods of photodynamic therapy, cytoluminescence therapy, or photodynamic diagnosis, for example, for the treatment or detection of tumors or antiviral treatment.

[0002] The structure of "chlorin e6" is shown below. [ka] [Background technology]

[0003] Porphyrins and their analogues are known photosensitive chemical compounds that can absorb photons and emit them at higher wavelengths. These unique properties have many applications, one of which is photodynamic therapy (PDT).

[0004] There are currently two generations of photosensitizers for PDT: the first generation contains heme porphyrins (blood derivatives), and the second generation is mostly chlorophyll analogues, the latter compounds known as chlorins and bacteriochlorins.

[0005] Chlorin e4 has been shown to exhibit good photosensitizing activity. It has also been shown to have protective effects against indomethacin-induced gastric lesions in rats and TAA- or CCl4-induced acute liver injury in mice. Therefore, it has been suggested that chlorin e4 may be a promising new drug candidate for anti-gastroenteritis and liver damage protection. International Publication No. 2009 / 040411 suggests the use of chlorin e4 zinc complexes in photodynamic therapy, and International Publication No. 2014 / 091241 suggests the use of chlorin e4 disodium in photodynamic therapy. [ka]

[0006] However, there is a continuing need for better photosensitizers. There is a need for compounds with high singlet oxygen quantum yields, and preferably compounds with strong photosensitizing properties in organic and aqueous media. There is also a need for compounds with high fluorescence quantum yields. Furthermore, there is a need for compounds and / or compositions that have higher phototoxicity, lower dark toxicity, good stability, good solubility, and / or are easily purified. Summary of the Invention

[0007] A first aspect of the present invention relates to a compound of formula (I) or a complex of formula (II): [ka] or a pharmaceutically acceptable salt thereof, wherein: -R 1 is -CH2OR 2 , -CH2SR 2 , -CH2S(O)R 2 , -CH2S(O)2R 2 , -CHN(R 2 )2, -R 2 , -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3or -C(S)-N(R 3 )2 is selected; -R 2 are each independently H, -C(O)R 4 , -C(O)-OR 4 , -C(O)-SR 4 , -C(O)-N(R 4 )2, -C(S)-OR 4 , -C(S)-SR 4 , -C(S)-N(R 4 )2, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α -NH(R β ), -R α -N(R β )2, -R α -X, -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y, -R α -[R 8 ]Y, -R α -[N(R 5 )2(R 5’ )], -R α -[P(R 5 )2(R 5’ )] or -R α -[R 8’ ] is selected from; -R 3 and -R 4 are independently -H, -R α -H, -R β , -R α -R β , -R α -OH, -R α -ORβ , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α -NH(R β ), -R α -N(R β )2, -R α -X, -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y, -R α -[R 8 ]Y, -R α -[N(R 5 )2(R 5’ )], -R α -[P(R 5 )2(R 5’ )] or R α -[R 8’ ] is selected from; -R α - are each independently C1-C 42 alkylene groups, which can be optionally substituted with one or more (e.g., 1, 2, 3, 4, or 5) C-C alkyl, C-C haloalkyl, or halo groups, and one or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) carbon atoms in the backbone of the alkylene group can be optionally substituted with a heteroatom or group independently selected from O, S, NH, or NMe; -R β are each independently a saturated or unsaturated hydrocarbyl group which may be linear or branched or may be or include a cyclic group which may optionally be substituted and which may optionally include one or more (e.g., 1, 2, 3, 4 or 5) heteroatoms N, O, S, P or Se in its carbon skeleton; -R 5are each independently C1-C4 alkyl, C1-C4 haloalkyl, -(CH2CH2O) n -H, -(CH2CH2O) n and —CH, phenyl, or C-C heteroaryl, where phenyl or C-C heteroaryl optionally includes one or more (e.g., 1, 2, 3, 4, or 5) C-C alkyl, C-C haloalkyl, —O(C-C alkyl), —O(C-C haloalkyl), halo, —COH, —COZ, —CONH, —O—(CHCHO). n -H or -O-(CH2CH2O) n optionally substituted with -CH3 groups; -R 5’ is C1-C4 alkyl, C1-C4 haloalkyl, -(CH2CH2O) n -H, -(CH2CH2O) n -CH3, phenyl or C5-C6 heteroaryl, each selected from -CO2 - and the phenyl or C5-C6 heteroaryl is optionally substituted with one or more (e.g., 1, 2, 3, or 4) C1-C6 alkyl, C1-C6 haloalkyl, —O(C1-C6 alkyl), —O(C1-C6 haloalkyl), halo, —CO2H, —CO2Z, —CO2NH2, —O—(CH2CHO) n -H or -O-(CH2CH2O) n may be further substituted with -CH3 groups; -R 6 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2 is selected; -R 7 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R3 )2 is selected; -R 8 is one or more (e.g., 1, 2, 3, 4, or 5) C1-C6 alkyl, C1-C6 haloalkyl, -O(C1-C6 alkyl), -O(C1-C6 haloalkyl), halo, -CO2H, -CO2Z, -CO2NH2, -O-(CH2CH2O) n -H or -O-(CH2CH2O) n -[NC5H5] optionally substituted with -CH3 groups; -R 8’ is -CO2 - and optionally substituted with one or more (e.g., 1, 2, 3, or 4) C-C alkyl, C-C haloalkyl, —O(C-C alkyl), —O(C-C haloalkyl), halo, —COH, —COZ, —CONH, —O—(CHCHO) n -H or -O-(CH2CH2O) n -[NC5H5] further substituted with -CH3 groups; n is 1, 2, 3, 4, 5 or 6; X is a halo group; Y is a counter anion; Z is a counter cation; and M 2+ is a metal cation; However, the compound or complex is (1) (7S,8S)-7-(2-carboxyethyl)-5-(carboxymethyl)-18-ethyl-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-3-carboxylic acid [chlorin e6]; (2) (7S,8S)-18-ethyl-5-(2-methoxy-2-oxoethyl)-7-(3-methoxy-3-oxopropyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-3-carboxylic acid; (3) 2-((7S,8S)-18-ethyl-7-(3-methoxy-3-oxopropyl)-3-(methoxycarbonyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-5-yl)acetic acid; (4) 3-((7S,8S)-18-ethyl-5-(2-methoxy-2-oxoethyl)-3-(methoxycarbonyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-7-yl)propanoic acid; (5) (7S,8S)-5-(carboxymethyl)-18-ethyl-7-(3-methoxy-3-oxopropyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-3-carboxylic acid; (6) (7S,8S)-7-(2-carboxyethyl)-18-ethyl-5-(2-methoxy-2-oxoethyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-3-carboxylic acid; (7) 3-((7S,8S)-5-(carboxymethyl)-18-ethyl-3-(methoxycarbonyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-7-yl)propanoic acid; (8) Methyl (7S,8S)-18-ethyl-5-(2-methoxy-2-oxoethyl)-7-(3-methoxy-3-oxopropyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-3-carboxylate [chlorin e6 trimethyl ester]; (9) methyl 3-(3-carbamoyl-18-ethyl-5-(2-methoxy-2-oxoethyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-7-yl)propanoate; (10) methyl 3-(18-ethyl-5-(2-methoxy-2-oxoethyl)-2,8,12,17-tetramethyl-3-(methylcarbamoyl)-13-vinyl-7H,8H-porphyrin-7-yl)propanoate; (11) methyl 3-(18-ethyl-3-(ethylcarbamoyl)-5-(2-methoxy-2-oxoethyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-7-yl)propanoate; (12) methyl 3-(3-(benzoylcarbamoyl)-18-ethyl-5-(2-methoxy-2-oxoethyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-7-yl)propanoate; (13) methyl 3-(18-ethyl-5-(2-methoxy-2-oxoethyl)-2,8,12,17-tetramethyl-3-(piperidine-1-carbonyl)-13-vinyl-7H,8H-porphyrin-7-yl)propanoate; (14) 5-(2-((3-((5-amino-1-carboxypentyl)carbamoyl)-17-(carboxymethyl)-14-(3-guanidinopropyl)-20-(hydroxymethyl)-1,9,12,15,18,21-hexaoxodocosahydro-7H-pyrrolo[2,1-g][1,2]dithia[5,8,11,14,17,20]hexaazacyclotricosin-8-yl)amino)-2-oxoethyl)-7-(2-carboxyethyl)-18-ethyl-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-3-carboxylic acid; (15) (4-((2-(2-(3-carboxy-7-(2-carboxyethyl)-18-ethyl-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-5-yl)acetamido)ethyl)amino)-4-oxobutyl)triphenylphosphonium chloride; (16) (1-(3-carboxy-5-(2,13-dioxo-16-(triphenylphosphonio)-6,9-dioxa-3,12-diazahexadecyl)-18-ethyl-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-7-yl)-3,14-dioxo-7,10-dioxa-4,13-diazaheptadecan-17-yl)triphenylphosphonium dichloride; or a salt thereof.

[0008] A second aspect of the present invention provides a compound of formula (I) or a complex of formula (II) according to the first aspect of the present invention for use in medicine.

[0009] In the context of this specification, a "hydrocarbyl" substituent or hydrocarbyl moiety in a substituent contains only carbon and hydrogen atoms, but does not contain any heteroatoms such as N, O, S, P, or Se in its carbon skeleton, unless otherwise specified. Hydrocarbyl groups / moieties can be saturated or unsaturated (including aromatic), straight-chain or branched, or can be or contain cyclic groups, and unless otherwise specified, cyclic groups do not contain heteroatoms such as N, O, S, P, or Se in its carbon skeleton. Examples of hydrocarbyl groups include alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and aryl groups / moieties, and all combinations of these groups / moieties. Typically, hydrocarbyl groups are C1-C 60 Hydrocarbyl groups, more typically C1-C 40 Hydrocarbyl groups, more typically C1-C 20 More typically, the hydrocarbyl group is a C-C 12 More typically, the hydrocarbyl group is a C-C 10 A "hydrocarbylene" group is defined as a divalent hydrocarbyl group.

[0010] An "alkyl" substituent or alkyl moiety in a substituent can be linear (i.e., straight-chain) or branched. Examples of alkyl groups / moieties include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, and n-pentyl groups / moieties. Unless otherwise specified, the term "alkyl" does not include "cycloalkyl." Typically, alkyl groups are C1-C 12 An alkyl group is a C1-C6 alkyl group. More typically, the alkyl group is a C1-C6 alkyl group. An "alkylene" group is defined similarly as a divalent alkyl group. Typically, an alkylene group is a C1-C6 alkyl group. 42 More typically, the alkylene group is a C-C 32 Alkylene group, or C1-C 22 Alkylene group, or C1-C 12 It is an alkylene group.

[0011] An "alkenyl" substituent or alkenyl moiety in a substituent refers to an unsaturated alkyl group or moiety having one or more carbon-carbon double bonds. Examples of alkenyl groups / moieties include ethenyl, propenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, 1,3-butadienyl, 1,3-pentadienyl, 1,4-pentadienyl, and 1,4-hexadienyl groups / moieties. Unless otherwise specified, the term "alkenyl" does not include "cycloalkenyl." Typically, alkenyl groups are C2-C6 12 An alkenyl group. More typically, the alkenyl group is a C2-C6 alkenyl group. An "alkenylene" group is defined similarly as a divalent alkenyl group.

[0012] An "alkynyl" substituent or alkynyl moiety in a substituent refers to an unsaturated alkyl group or moiety having one or more carbon-carbon triple bonds. Examples of alkynyl groups / moieties include ethynyl, propargyl, but-1-ynyl, and but-2-ynyl. Typically, an alkynyl group is a C2-C 12 It is an alkynyl group. More typically, the alkynyl group is a C2-C6 alkynyl group. An "alkynylene" group is defined similarly as a divalent alkynyl group.

[0013] A "cyclic" substituent or cyclic moiety in a substituent refers to any hydrocarbyl ring, which may be saturated or unsaturated (including aromatic) and may contain one or more heteroatoms, such as N, O, S, P, or Se, in its carbon skeleton. Examples of cyclic groups include cycloalkyl, cycloalkenyl, heterocyclic, aryl, and heteroaryl groups, discussed below. Cyclic groups may be monocyclic, bicyclic (e.g., bridged, fused, or spiro), or polycyclic. Typically, cyclic groups are 3- to 12-membered cyclic groups, meaning they contain 3 to 12 ring atoms. More typically, cyclic groups are 3- to 7-membered monocyclic groups, meaning they contain 3 to 7 ring atoms.

[0014] A "heterocyclic" substituent or heterocyclic moiety in a substituent refers to a cyclic group or moiety that includes one or more carbon atoms and one or more (e.g., 1, 2, 3, or 4) heteroatoms, such as N, O, S, P, or Se, in the ring structure. Examples of heterocyclic groups include the heteroaryl groups discussed below, as well as non-aromatic heterocyclic groups such as azetidinyl, azetinyl, tetrahydrofuranyl, pyrrolidinyl, tetrahydrothiophenyl, tetrahydropyranyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, oxetanyl, thietanyl, pyrazolidinyl, imidazolidinyl, dioxolanyl, oxathiolanyl, thianyl, and dioxanyl groups.

[0015] A "cycloalkyl" substituent or cycloalkyl moiety in a substituent refers to a saturated hydrocarbyl ring containing, for example, 3 to 7 carbon atoms, examples of which include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Unless otherwise specified, a cycloalkyl substituent or moiety can include monocyclic, bicyclic, or polycyclic hydrocarbyl rings.

[0016] A "cycloalkenyl" substituent or cycloalkenyl moiety in a substituent refers to a non-aromatic unsaturated hydrocarbyl ring having one or more carbon-carbon double bonds and containing, for example, 3 to 7 carbon atoms, examples of which include cyclopent-1-en-1-yl, cyclohex-1-en-1-yl, and cyclohexa-1,3-dien-1-yl. Unless otherwise specified, a cycloalkenyl substituent or moiety can include monocyclic, bicyclic, or polycyclic hydrocarbyl rings.

[0017] An "aryl" substituent or aryl moiety in a substituent refers to an aromatic hydrocarbyl ring. The term "aryl" includes monocyclic aromatic hydrocarbons and polycyclic fused-ring aromatic hydrocarbons, in which all of the fused ring systems (excluding ring systems that are part of or formed by any substituent) are aromatic. Examples of aryl groups / moieties include phenyl, naphthyl, anthracenyl, and phenanthrenyl. Unless otherwise specified, the term "aryl" does not include "heteroaryl."

[0018] A "heteroaryl" substituent or heteroaryl moiety in a substituent refers to an aromatic heterocyclic group or moiety. The term "heteroaryl" includes monocyclic aromatic heterocycles and polycyclic fused-ring aromatic heterocycles, in which all of the fused ring systems (excluding ring systems that are part of or formed by any substituent) are aromatic. Examples of heteroaryl groups / moieties include: [ka] where G=O, S or NH.

[0019] For purposes of this specification, when a combination of moieties is referred to as a group, e.g., arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl, or alkynylaryl, the last-mentioned moiety includes the atoms of the remainder of the molecule to which the group is attached. An example of an arylalkyl group is benzyl.

[0020] For purposes of this specification, an optionally substituted group or moiety (—R β etc.): (i) each hydrogen atom is optionally replaced by halo; -CN; -NO; -N; -R x ;-OH;-OR x ;-R y -Haro;-R y -CN;-R y -NO2;-R y -N3;-R y -R x ;-R y -OH;-R y -OR x ;-SH;-SR x ;-SOR x ;-SO2H;-SO2R x ;-SO2NH2;-SO2NHR x ;-SO2N(R x )2;-R y -SH;-R y -SR x ;-R y -SORx ;-R y -SO2H;-R y -SO2R x ;-R y -SO2NH2;-R y -SO2NHR x ;-R y -SO2N(R x )2;-NH2;-NHR x ;-N(R x )2;-N + (R x )3;-R y -NH2;-R y -NHR x ;-R y -N(R x )2;-R y -N + (R x )3;-CHO;-COR x ;-COOH;-COOR x ;-OCOR x ;-R y -CHO;-R y -COR x ;-R y -COOH;-R y -COOR x ; or -R y -OCOR x and / or may be substituted with monovalent substituents independently selected from (ii) Any two hydrogen atoms attached to the same carbon atom are oxo (=O), =S, =NH, or =NR x and / or (iii) Any two hydrogen atoms bonded to the same or different atoms within the same optionally substituted group or moiety may be replaced by —O—, —S—, —NH—, —N(R x )-, -N + (R x )2- or -R y -, and optionally substituted with a bridging substituent independently selected from where each -R y- is independently selected from an alkylene, alkenylene, or alkynylene group which contains 1 to 6 atoms in its backbone; one or more carbon atoms in the backbone of an alkylene, alkenylene, or alkynylene group can optionally be replaced with one or more heteroatoms N, O, or S; and the alkylene, alkenylene, or alkynylene group can optionally contain one or more halo and / or -R x groups; and Each-R x are independently selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, or C2-C6 cyclic groups, or any two or three -R attached to the same nitrogen atom x may form a C2-C7 cyclic group together with the nitrogen atom to which they are attached, and any -R x can be optionally substituted with one or more C1-C4 alkyl, C1-C4 haloalkyl, —O(C1-C4 alkyl), —O(C1-C4 haloalkyl), halo, —OH, —NH2, —CN, or oxo (═O) groups.

[0021] Typically, the substituents include 1, 2, 3 or 4 substituents, more typically 1, 2 or 3 substituents, more typically 1 or 2 substituents, more typically 1 substituent.

[0022] Unless otherwise specified, any divalent bridging substituent (e.g., —O—, —S—, —NH—, —N(R x )-, -N + (R x )2- or -R y The -) must be attached only to the specified group or moiety, and cannot be attached to a second group or moiety, even if that second group or moiety itself may be optionally substituted.

[0023] The term "halo" includes fluoro, chloro, bromo and iodo.

[0024] Unless otherwise specified, when a group is prefixed with the term "halo," such as a haloalkyl or halomethyl group, it is understood that the group in question is substituted with one or more halo groups independently selected from fluoro, chloro, bromo, and iodo. Typically, the maximum number of halo substituents is limited only by the number of hydrogen atoms available for substitution in the corresponding group without the halo prefix. For example, a halomethyl group may contain one, two, or three halo substituents. A haloethyl or halophenyl group may contain one, two, three, four, or five halo substituents. Similarly, unless otherwise specified, when a group begins with a particular halo group, it is understood that the group in question is substituted with one or more of the specified halo groups. For example, the term "fluoromethyl" refers to a methyl group substituted with one, two, or three fluoro groups.

[0025] Unless otherwise specified, when a group is referred to as "halo-substituted," it is understood that the group in question is substituted with one or more halo groups independently selected from fluoro, chloro, bromo, and iodo. Typically, the maximum number of halo substituents is limited only by the number of hydrogen atoms available for substitution in the group referred to as halo-substituted. For example, a halo-substituted methyl group may contain one, two, or three halo substituents. A halo-substituted ethyl or halo-substituted phenyl group may contain one, two, three, four, or five halo substituents.

[0026] Unless otherwise specified, a reference to an element is considered to be a reference to all isotopes of that element, so for example, unless otherwise specified, a reference to hydrogen is considered to encompass all isotopes of hydrogen, including deuterium and tritium.

[0027] Unless otherwise stated, a reference to a compound or group should be understood to refer to all tautomeric forms of that compound or group.

[0028] When referring to a hydrocarbyl or other group that contains one or more heteroatoms N, O, S, P or Se in its carbon skeleton, or to a carbon atom of a hydrocarbyl or other group that is substituted by an N, O, S, P or Se atom, what is intended is: [ka] teeth, [ka] or [ka] is replaced by; -CH2- is replaced by -NH-, -PH-, -O-, -S- or -Se-; -CH3 is replaced by -NH2, -PH2, -OH, -SH, or -SeH; -CH= is replaced by -N= or -P=; -CH2- is replaced by -NH-, -PH-, -O-, -S- or -Se-; or CH≡ is replaced by N≡ or P≡; provided that the resulting group contains at least one carbon atom. For example, methoxy, dimethylamino, and aminoethyl groups are considered to be hydrocarbyl groups containing one or more heteroatoms N, O, S, P, or Se in their carbon skeleton.

[0029] In the context of this specification, unless otherwise stated, C x -C y A group is defined as a group containing x to y carbon atoms. For example, a C1-C4 alkyl group is defined as an alkyl group containing 1 to 4 carbon atoms. When calculating the total number of carbon atoms in a parent group, including any substituted and / or moieties, optional substituents and moieties are not taken into account. For the avoidance of doubt, substituted heteroatoms, e.g., N, O, S, P, or Se, are not included in the C x -C yWhen calculating the number of carbon atoms in a group, they should be counted as carbon atoms. For example, a morpholinyl group should be considered a C6 heterocyclic group, not a C4 heterocyclic group.

[0030] Because the pi electrons of the chlorin ring are delocalized, the chlorin ring can be represented by multiple resonance structures. Resonance structures are different ways of depicting the same compound. Two of the resonance structures of the chlorin ring are shown directly below: [ka]

[0031] Typically, a complex contains a central metal atom or ion, known as a coordination center, and a binding molecule or ion, known as a ligand. Typically, a complex contains a central metal atom or ion, known as a coordination center, and a binding molecule or ion, known as a ligand. Herein, the bond between the coordination center and the ligand is represented as shown in the complex below on the left (the attraction between the anionic ligand and the central metal cation is represented by four dashed lines), but equivalently, it can be represented as shown in the complex below on the right (the attraction between the ligand molecule and the central metal atom is represented by two covalent bonds and two dashed lines): [ka]

[0032] As used herein, -[NC5H5]Y refers to: [ka]

[0033] In one embodiment of the first or second aspect of the invention, X is a halo group selected from fluoro, chloro, bromo, or iodo. In one embodiment, X is chloro or bromo.

[0034] In one embodiment of the first or second aspect of the present invention, there is provided a compound of formula (I):

[0035] In one embodiment of the first or second aspect of the invention, Y is a halide (e.g., fluoride, chloride, bromide, or iodide) or other inorganic anion (e.g., bisulfate, hexafluorophosphate (PF6), nitrate, perchlorate, sulfate, bisulfate, or phosphate) or an organic anion (e.g., acetate, ascorbate, aspartate, benzoate, besylate (benzenesulfonate), bicarbonate, bis(trifluoromethanesulfonyl)imide (TFSI), acid tartrate, butyrate, camsylate (camphorsulfonate), carbonate, citrate, decanoate, edetate, esylate (ethanesulfonate), fumarate, galactarate, gluceptate, gluconate, glutamate, glycolate, hexanoate, β-hydroxybutyrate, 2-hydroxyethanesulfonate, and the counteranion is selected from hydroxymaleate, hydroxynaphthoate, isethionate, lactate, lactobionate, malate, maleate, mandelate, mesylate (methanesulfonate), methylsulfate, mucate, napsylate (naphthalene-2-sulfonate), octanoate, oleate, ornithine, pamoate, pantothenate, polygalacturonate, propanoate, propionate, salicylate, stearate, succinate, tartrate, teoclate, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BARF), tetrakis(pentafluorophenyl)borate (F5-TPB), tetraphenylborate (TPB), tosylate (toluene-p-sulfonate), or triflate (trifluoromethanesulfonate).

[0036] In another embodiment of the first or second aspect of the invention, Y is a halide (e.g., fluoride, chloride, bromide, or iodide) or other inorganic anion (e.g., bisulfate, nitrate, perchlorate, phosphate, or sulfate) or an organic anion (e.g., acetate, aspartate, benzoate, besylate (benzenesulfonate), butyrate, camsylate (camphorsulfonate), citrate, esylate (ethanesulfonate), fumarate, galactarate, gluconate, or the like). , glutamate, glycolate, 2-hydroxyethanesulfonate, hydroxymaleate, lactate, malate, maleate, mandelate, mesylate (methanesulfonate), napsylate (naphthalene-2-sulfonate), ornithine, pamoate, pantothenate, propanoate, salicylate, succinate, tartrate, tosylate (toluene-p-sulfonate), or triflate (trifluoromethanesulfonate). In one embodiment, Y is fluoride, chloride, bromide, or iodide. In one embodiment, Y is chloride or bromide.

[0037] In one embodiment of the first or second aspect of the invention, Z is a counter cation selected from an inorganic cation (e.g., lithium, sodium, potassium, magnesium, calcium, or ammonium cation) or an organic cation (e.g., an amine cation (e.g., choline or meglumine cation) or an amino acid cation (e.g., arginine cation)).

[0038] In one embodiment of the first or second aspect of the invention, M 2+ Zn 2+ , Cu 2+ , Fe 2+ , Pd 2+ or Pt 2+ In one embodiment, M 2+ is Zn 2+ is.

[0039] In one embodiment of the first or second aspect of the invention, -R 1is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2. In one embodiment, -R 1 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2 or -C(S)-N(R 3 )2. In one embodiment, -R 1 is -C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )2 is selected.

[0040] In one embodiment of the first or second aspect of the invention, -R 1 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2, each of which is selected from -R 3 is C1-C4 alkyl (preferably methyl). In one embodiment, -R 1 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2 or -C(S)-N(R 3 )2, each of which is selected from -R 3 is C1-C4 alkyl (preferably methyl). In one embodiment, -R 1 is -C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )2, each of which is selected from -R 3 is C1-C4 alkyl (preferably methyl). In one embodiment, -R 1 is -C(O)-OR3 and -R 3 is C1-C4 alkyl (preferably methyl).

[0041] In one embodiment of the first or second aspect of the invention, -R 1 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2, each of which is selected from -R 3 -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group. In one embodiment, -R 1 is -C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )2, each of which is selected from -R 3 -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group. In one embodiment, -R 1 is -C(O)-OR 3 or -C(O)-SR 3 -R 3 -R α -OR β or -R α -SR β -R β is a saccharidyl group. Typically, in these embodiments, -R α - is C1-C 12an alkylene group (preferably a C1-C8 alkylene group or a C1-C6 alkylene group), —(CH2CH2O) m - group or -(CH2CH2S) m - groups, all of which are optionally substituted, where m is 1, 2, 3, or 4.

[0042] In one embodiment of the first or second aspect of the invention, -R 1 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )(R 3’ ) or -C(S)-N(R 3 )(R 3’ ), where -R 3 -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl (preferably methyl). In one embodiment, -R 1 is -C(O)-N(R 3 )(R 3’ ) where -R 3 -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl (preferably methyl). In one embodiment, -R 1 is -C(O)-N(R 3 )(R 3’ ) where -R 3 -R α -ORβ or -R α -SR β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl (preferably methyl). In one embodiment, -R 1 is -C(O)-N(R 3 )(R 3’ ) and -R 3 -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group, and -R 3’ is C1-C4 alkyl (preferably methyl). In one embodiment, -R 1 is -C(O)-N(R 3 )(R 3’ ) where -R 3 -R α -OR β or -R α -SR β -R β is a saccharidyl group, and -R 3’ is C1-C4 alkyl (preferably methyl). Typically, in these embodiments, -R α - is C1-C 12 an alkylene group (preferably a C1-C8 alkylene group or a C1-C6 alkylene group), —(CH2CH2O) m - group or -(CH2CH2S) m - groups, all of which are optionally substituted, where m is 1, 2, 3, or 4.

[0043] -R 3’ The group is another -R 3 -R bonded to the same atom as the group 3 -R refers to the group 3 and -R 3’ may be the same or different. Preferably, -R3 and -R 3’ is different.

[0044] In one embodiment of the first and second aspects of the present invention, -R 1 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )(R 3’ ) or -C(S)-N(R 3 )(R 3’ ), where -R 3 -R α -R β or -R β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl (preferably methyl). In one embodiment, -R 1 is -C(O)-N(R 3 )(R 3’ ) where -R 3 -R α -R β or -R β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl (preferably methyl). Typically, in these embodiments, -R α - is C1~C 12 an alkylene group (preferably a C1-C8 alkylene group or a C1-C6 alkylene group), —(CH2CH2O) m - group or -(CH2CH2S) m - groups, all of which are optionally substituted, where m is 1, 2, 3, or 4.

[0045] In any of the embodiments of the previous four paragraphs, the saccharidyl group may optionally be substituted, for example, with a protecting group such as acetyl or a natural amino acid such as valine. The amino acid may be attached to the saccharidyl group, for example, by forming an ester between the carboxylic acid group of the amino acid and the hydroxyl group of the saccharidyl group.

[0046] In one embodiment of the first and second aspects of the present invention, -R 1 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )(R 3’ ) or -C(S)-N(R 3 )(R 3’ ), where -R 3 -R α -R β or -R β -R β is a C1-C8 alkyl group optionally substituted with one or more (e.g., 1, 2, 3, 4, 5, 6, 7, or 8) hydroxyl groups, and -R 3’ is H or C1-C4 alkyl (preferably methyl). In one embodiment, -R 1 is -C(O)-N(R 3 )(R 3’ ) where -R 3 Ha-R α -R β or -R β -R β is a C1-C8 alkyl group optionally substituted with one or more (e.g., 1, 2, 3, 4, 5, 6, 7, or 8) hydroxyl groups, and -R 3’ is H or C1-C4 alkyl (preferably methyl). Typically, in these embodiments, -R α - is an unsubstituted C1-C6 alkylene group, or an unsubstituted C1-C4 alkylene group, or an unsubstituted C1-C2 alkylene group.

[0047] In one embodiment of the first or second aspect of the invention, -R 1 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )(R 3’ ) or -C(S)-N(R 3 )(R 3’ ) and -R 3 -R α -H or -R α-OH, -R α - is C1-C 12 alkylene groups, where the alkylene groups can be optionally substituted with one or more C-C alkyl, C-C haloalkyl, or halo groups, and one or more carbon atoms in the backbone of the alkylene group can be optionally replaced with one or more heteroatoms O or S; -R 3’ is H or C1-C4 alkyl (preferably methyl). In one embodiment, -R 1 is -C(O)-N(R 3 )(R 3’ ) where -R 3 -R α -H or -R α -OH, -R α - is C1-C 12 alkylene groups, wherein one or more carbon atoms in the backbone of the alkylene group can be optionally replaced by one or more heteroatoms O or S; 3’ is H or C1-C4 alkyl (preferably methyl).

[0048] In one embodiment of the first and second aspects of the present invention, -R 1 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )(R 3’ ) or -C(S)-N(R 3 )(R 3’ ), where -R 3 Ha-R β and -R β are independently halo, -CN, -NO2, -N3, -OH, -OR x , -SH, -SR x , -SOR x , -SO2H, -SO2R x , -SO2NH2, -SO2NHR x , -SO2N(R x )2, -NH2, -NHR x , -N(R x )2, -N + (R x )3, -CHO, -CORx , -COOH, -COOR x , -OCOR x or -NH-CO-CR z C1-C optionally substituted with one or more (e.g., 1, 2, 3, 4, or 5) substituents selected from —NH2 12 is an alkyl group, and each -R x is independently selected from C1-C4 alkyl, -R z is the side chain of a natural amino acid, and -R 3’ is H or C1-C4 alkyl (preferably methyl). In one embodiment, -R 1 is -C(O)-N(R 3 )(R 3’ ) where -R 3 Ha-R β and -R β are independently halo, -CN, -NO2, -N3, -OH, -OR x , -SH, -SR x , -SOR x , -SO2H, -SO2R x , -SO2NH2, -SO2NHR x , -SO2N(R x )2, -NH2, -NHR x , -N(R x )2, -N + (R x )3, -CHO, -COR x , -COOH, -COOR x , -OCOR x or -NH-CO-CR z -NH2, wherein each -R x is independently selected from C1-C4 alkyl, -R z is the side chain of a natural amino acid, and -R 3’ is H or C1-C4 alkyl (preferably methyl).

[0049] In one embodiment of the first and second aspects of the present invention, -R 1 is -C(O)-OR 3 , -C(O)-SR3 , -C(O)-N(R 3 )(R 3’ ) or -C(S)-N(R 3 )(R 3’ ), where -R 3 -R α -[P(R 5 )3]Y, and each -R 5 is independently selected from phenyl or C5-C6 heteroaryl, wherein phenyl or C5-C6 heteroaryl is optionally selected from one or more of C1-C4 alkyl, C1-C4 haloalkyl, —O(C1-C4 alkyl), —O(C1-C4 haloalkyl), halo, —O—(CH2CHO) n -H or -O-(CH2CH2O) n -CH3 groups, n is 1, 2, 3 or 4, Y is fluoride, chloride, bromide or iodide, -R 3’ is H or C1-C4 alkyl (preferably methyl). In one embodiment, -R 1 is -C(O)-N(R 3 )(R 3’ ) where -R 3 -R α -[P(R 5 )3]Y, and each -R 5 is independently selected from phenyl or C5-C6 heteroaryl, wherein phenyl or C5-C6 heteroaryl is optionally selected from one or more of C1-C4 alkyl, C1-C4 haloalkyl, —O(C1-C4 alkyl), —O(C1-C4 haloalkyl), halo, —O—(CH2CHO) n -H or -O-(CH2CH2O) n -CH3 groups, n is 1, 2, 3 or 4, Y is fluoride, chloride, bromide or iodide, -R 3’ is H or C1-C4 alkyl (preferably methyl). Typically, in these embodiments, -R α - is C1-C 12 an alkylene group (preferably a C1-C8 alkylene group or a C1-C6 alkylene group), —(CH2CH2O) m - group or -(CH2CH2S)m - groups, all of which are optionally substituted, where m is 1, 2, 3, or 4.

[0050] In one embodiment of the first or second aspect of the invention, -R 1 -C(O)-OR 3 where -R 3 is selected from C1-C4 alkyl (preferably methyl), or a cation (such as lithium, sodium, potassium, magnesium, calcium, ammonium, an amine (such as choline or meglumine) or an amino acid (such as arginine) cation).

[0051] In one embodiment of the first or second aspect of the invention, -R 1 is -C(O)-N(R 3 )2. In one embodiment, -R 1 is -C(O)-N(C1-C4 alkyl)(R 3 ) or -C(O)-NHR 3 In one embodiment, -R 1 is -C(O)-N(CH3)(R 3 ) or -C(O)-NHR 3 In one embodiment, -R 1 is -C(O)-N(C1-C4 alkyl)(R 3 In one embodiment, -R 1 is -C(O)-N(CH3)(R 3 )

[0052] In one embodiment of the first or second aspect of the invention, -R 1 is -CH2OR 2 , -CH2SR 2 , -CH2S(O)R 2 , -CH2S(O)2R 2 , -CHN(R 2 )2 or -R 2 In one embodiment, -R 1 is -CH2OR 2 , -CH2SR 2 , -CHN(R 2 )2 or -R2 In one embodiment, -R 1 is -CH2OR 2 , -CH2SR 2 or -CHN(R 2 )2. In one embodiment, -R 1 is -CH2OR 2 or -CH2SR 2 In one embodiment, -R 1 is -CH2OR 2 In one embodiment, -R 1 Ha-R 2 and -R 2 Ha-R α -X.

[0053] In one embodiment of the first or second aspect of the invention, -R 2 -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α -NH(R β ), -R α -N(R β )2, -R α -X, -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y or -R α In one embodiment, -R 2 -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2Rβ In one embodiment, each -R 2 -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group. In one embodiment, -R 2 -R α -OR β or -R α -SR β In one embodiment, -R 2 -R α -OR β or -R α -SR β -R β is a saccharidyl group.

[0054] In one embodiment of the first or second aspect of the invention, -R 2 is -C(O)R 4 , -C(O)-OR 4 , -C(O)-SR 4 , -C(O)-N(R 4 )2, -C(S)-OR 4 , -C(S)-SR 4 or -C(S)-N(R 4 )2. In one embodiment, -R 2 is -C(O)R 4 , -C(O)-OR 4 , -C(O)-SR 4 , -C(O)-N(R 4 )2 or -C(S)-N(R 4 )2. In one embodiment, -R 2 is -C(O)R 4 , -C(O)-OR 4 , -C(O)-SR 4 or -C(O)-N(R 4 )2 is selected.

[0055] In one embodiment of the first or second aspect of the invention, -R 2 is -C(O)-N(R 4 )(R 4’ ) and -R 4 -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group, and -R 4’ is H or C1-C4 alkyl (preferably methyl). In one embodiment, -R 2 is -C(O)-N(R 4 )(R 4’ ) and -R 4 -R α -OR β or -R α -SR β -R β is a saccharidyl group, and -R 4’ is H or C1-C4 alkyl (preferably methyl). In one embodiment, -R 2 is -C(O)-N(R 4 )(R 4’ ) and -R 4 -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group, and -R 4’ is C1-C4 alkyl (preferably methyl). In one embodiment, -R 2 is -C(O)-N(R 4 )(R 4’ ) and -R 4 -R α -OR β or -R α -SR β -Rβ is a saccharidyl group, and -R 4’ is C1-C4 alkyl (preferably methyl).

[0056] -R 4’ The group is another -R 4 -R bonded to the same atom as the group 4 -R refers to the group 4 and -R 4’ may be the same or different. Preferably, -R 4 and -R 4’ is different.

[0057] In one embodiment of the first or second aspect of the invention, -R 2 is -C(O)-N(R 4 )2. In one embodiment, -R 2 is -C(O)-N(C1-C4 alkyl)(R 4 In one embodiment, -R 2 is -C(O)-N(CH3)(R 4 )

[0058] In one embodiment of the first or second aspect of the invention, -R 6 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2, each of which is selected from -R 3 is C1-C4 alkyl, and preferably each -R 3 is methyl. In one embodiment, -R 6 is -C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )2, each of which is selected from -R 3 is C1-C4 alkyl, and preferably each -R 3 is methyl. In one embodiment, -R 6 -C(O)-OR 3 and -R 3is C1-C4 alkyl, preferably -R 3 is methyl.

[0059] In one embodiment of the first or second aspect of the invention, -R 6 -C(O)-OR 3 and -R 3 is selected from hydrogen, C1-C4 alkyl (preferably methyl), or a cation (e.g., lithium, sodium, potassium, magnesium, calcium, ammonium, an amine (e.g., choline or meglumine), or an amino acid (e.g., arginine) cation).

[0060] In one embodiment of the first or second aspect of the invention, -R 6 is C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(O)-N(R 3 )(R 3’ ), -C(S)-OR 3 , -C(S)-SR 3 , -C(S)-N(R 3 )2 or -C(S)-N(R 3 )(R 3’ ) and -R 3 Ha-R β and -R β is C1-C 20 alkyl groups, wherein the alkyl group is optionally substituted with 1, 2, 3, or 4 halo groups, and wherein 1, 2, 3, 4, 5, or 6 carbon atoms in the backbone of the alkyl group are optionally replaced with heteroatoms or groups independently selected from O, S, NH, or NMe; -R 3’ is H or C1-C4 alkyl (preferably methyl).

[0061] In one embodiment of the first or second aspect of the invention, -R 6 is C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3, -C(S)-SR 3 or -C(S)-N(R 3 )2, each of which is selected from -R 3 -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group. In one embodiment, -R 6 is -C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )2, each of which is selected from -R 3 -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group. In one embodiment, -R 6 is -C(O)-OR 3 or -C(O)-SR 3 -R 3 -R α -OR β or -R α -SR β -R β is a saccharidyl group. Typically in these embodiments, -R α - is C1-C 12 alkylene groups, wherein 1, 2, 3, or 4 carbon atoms in the backbone of the alkylene group are optionally replaced with heteroatoms or groups independently selected from O, S, NH, or NMe. Alternatively, in these embodiments, -R α - is C1-C 12 an alkylene group (preferably a C1-C8 alkylene group or a C1-C6 alkylene group), —(CH2CH2O) m-CH2CH2- group or -(CH2CH2S) m -CH2CH2- groups, all of which are optionally substituted, where m is 1, 2, 3, or 4.

[0062] In one embodiment of the first or second aspect of the invention, -R 6 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )(R 3’ ) or -C(S)-N(R 3 )(R 3’ ), where -R 3 -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl (preferably methyl). In one embodiment, -R 6 is -C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )(R 3’ ), where -R 3 -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl (preferably methyl). In one embodiment, -R 6 is -C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )(R 3’), where -R 3 -R α -OR β or -R α -SR β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl (preferably methyl). Typically, in these embodiments, -R α - is C1-C 12 alkylene groups, wherein 1, 2, 3, or 4 carbon atoms in the backbone of the alkylene group are optionally replaced with heteroatoms or groups independently selected from O, S, NH, or NMe. Alternatively, in these embodiments, -R α - is C1-C 12 an alkylene group (preferably a C1-C8 alkylene group or a C1-C6 alkylene group), —(CH2CH2O) m -CH2CH2- group or -(CH2CH2S) m -CH2CH2- groups, all of which are optionally substituted, where m is 1, 2, 3, or 4.

[0063] -R 3’ The group is another -R 3 -R bonded to the same atom as the group 3 -R refers to the group 3 and -R 3’ may be the same or different. Preferably, -R 3 and -R 3’ is different.

[0064] In one embodiment of the first or second aspect of the invention, -R 6 is -C(O)-N(R 3 )2. In one embodiment, -R 6 is -C(O)-N(C1-C4 alkyl)(R 3 ) or -C(O)-NHR 3 In one embodiment, -R 6 is -C(O)-N(CH3)(R 3 ) or -C(O)-NHR 3 is.

[0065] In one embodiment of the first or second aspect of the invention, -R 7 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2, each of which is selected from -R 3 is C1-C4 alkyl, and preferably each -R 3 is methyl. In one embodiment, -R 7 is -C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )2, each of which is selected from -R 3 is C1-C4 alkyl, and preferably each -R 3 is methyl. In one embodiment, -R 7 -C(O)-OR 3 and -R 3 is C1-C4 alkyl, preferably -R 3 is methyl.

[0066] In one embodiment of the first or second aspect of the invention, -R 7 -C(O)-OR 3 and -R 3 is selected from hydrogen, C1-C4 alkyl (preferably methyl), or a cation (e.g., lithium, sodium, potassium, magnesium, calcium, ammonium, an amine (e.g., choline or meglumine), or an amino acid (e.g., arginine) cation).

[0067] In one embodiment of the first or second aspect of the invention, -R 7 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(O)-N(R 3 )(R 3’ ), -C(S)-OR3 , -C(S)-SR 3 , -C(S)-N(R 3 )2 or -C(S)-N(R 3 )(R 3’ ) and -R 3 Ha-R β and -R β is C1-C 20 alkyl groups, wherein the alkyl group is optionally substituted with 1, 2, 3, or 4 halo groups, and wherein 1, 2, 3, 4, 5, or 6 carbon atoms in the backbone of the alkyl group are optionally replaced with heteroatoms or groups independently selected from O, S, NH, or NMe; -R 3’ is H or C1-C4 alkyl (preferably methyl).

[0068] In one embodiment of the first or second aspect of the invention, -R 7 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2, each of which is selected from -R 3 -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group. In one embodiment, -R 7 is -C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )2, each of which is selected from -R 3 -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α-S(O)2R β -R β is a saccharidyl group. In one embodiment, -R 7 is -C(O)-OR 3 or -C(O)-SR 3 -R 3 -R α -OR β or -R α -SR β -R β is a saccharidyl group. Typically in these embodiments, -R α - is C1-C 12 alkylene groups, wherein 1, 2, 3, or 4 carbon atoms in the backbone of the alkylene group are optionally replaced with heteroatoms or groups independently selected from O, S, NH, or NMe. Alternatively, in these embodiments, -R α - is C1-C 12 an alkylene group (preferably a C1-C8 alkylene group or a C1-C6 alkylene group), —(CH2CH2O) m -CH2CH2- group or -(CH2CH2S) m -CH2CH2- groups, all of which are optionally substituted, where m is 1, 2, 3, or 4.

[0069] In one embodiment of the first or second aspect of the invention, -R 7 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )(R 3’ ) or -C(S)-N(R 3 )(R 3’ ) and -R 3 -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group, and -R3’ is H or C1-C4 alkyl (preferably methyl). In one embodiment, -R 7 is -C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )(R 3’ ) and -R 3 -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl (preferably methyl). In one embodiment, -R 7 is -C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )(R 3’ ) and -R 3 -R α -OR β or -R α -SR β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl (preferably methyl). Typically, in these embodiments, -R α - is C1-C 12 alkylene groups, wherein 1, 2, 3, or 4 carbon atoms in the backbone of the alkylene group are optionally replaced with heteroatoms or groups independently selected from O, S, NH, or NMe. Alternatively, in these embodiments, -R α - is C1-C 12 an alkylene group (preferably a C1-C8 alkylene group or a C1-C6 alkylene group), —(CH2CH2O) m -CH2CH2- group or -(CH2CH2S) m-CH2CH2- groups, all of which are optionally substituted, where m is 1, 2, 3, or 4.

[0070] -R 3’ The group is another -R 3 -R bonded to the same atom as the group 3 -R refers to the group 3 and -R 3’ may be the same or different. Preferably, -R 3 and -R 3’ is different.

[0071] In one embodiment of the first or second aspect of the invention, -R 7 is -C(O)-N(R 3 )2. In one embodiment, -R 7 is -C(O)-N(C1-C4 alkyl)(R 3 ) or -C(O)-NHR 3 In one embodiment, -R 7 is -C(O)-N(CH3)(R 3 ) or -C(O)-NHR 3 is.

[0072] In one embodiment of the first or second aspect of the invention, each -R α -Independently, C1-C 12 Alkylene group, -(CH2CH2O) m - group or -(CH2CH2S) m - groups, all optionally substituted, where m is 1, 2, 3, or 4. In one embodiment, each -R α -Independently, C1-C 12 Alkylene group or -(CH2CH2O) m - groups, both of which are optionally substituted, where m is 1, 2, 3, or 4. In one embodiment, each -R α - is independently an optionally substituted -(CH2CH2O) m - group, where m is 1, 2, 3 or 4.

[0073] In one embodiment of the first or second aspect of the invention, each -R α - is independently a C1-C8 alkylene group, or a C1-C6 alkylene group, or a C2-C4 alkylene group, all of which are optionally substituted.

[0074] In one embodiment of the first or second aspect of the invention, each -R α - is independently unsubstituted or substituted with one or more substituents independently selected from halo, C1-C4 alkyl, or C1-C4 haloalkyl. In one embodiment, each -R α - is independently unsubstituted or substituted with one or two substituents independently selected from halo, C1-C4 alkyl, or C1-C4 haloalkyl. In one embodiment, each -R α - is unsubstituted.

[0075] In one embodiment of the first and second aspects of the invention, each -R β are independently saturated or unsaturated hydrocarbyl groups which may be linear or branched or which may be or include cyclic groups, which may be optionally substituted, and which may optionally include one or more heteroatoms N, O or S in its carbon skeleton.

[0076] In one embodiment of the first or second aspect of the invention, at least one -R β is independently a C1-C6 alkyl group, or a C1-C4 alkyl group, or a methyl group, all of which are optionally substituted. In one embodiment, each -R β is independently a C1-C6 alkyl group, or a C1-C4 alkyl group, or a methyl group, all optionally substituted.

[0077] In one embodiment of the first or second aspect of the invention, at least one -R β is independently a saccharidyl group. In one embodiment, each -R β are independently saccharidyl groups.

[0078] In one embodiment of the first or second aspect of the invention, each -R β is independently unsubstituted or substituted with one or more substituents independently selected from halo, C-C alkyl, or C-C haloalkyl. In one embodiment, each -R β is independently unsubstituted or substituted with one or two substituents independently selected from halo, C-C alkyl, or C-C haloalkyl. In one embodiment, each -R β is non-substituted.

[0079] In one embodiment of the first and second aspects of the invention, each -R 3 independently, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α -NH(R β ), -R α -N(R β )2, -R α -X, -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y or -R α -[NC5H5]Y. In one embodiment, each -R 3 independently, -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R βIn one embodiment, each -R 3 independently, -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group. In one embodiment, each -R 3 independently, -R α -OR β or -R α -SR β In one embodiment, each -R 3 independently, -R α -OR β or -R α -SR β -R β is a saccharidyl group.

[0080] In one embodiment of the first and second aspects of the invention, each -R 4 independently, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α -NH(R β ), -R α -N(R β )2, -R α -X, -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y or -R α -[NC5H5]Y. In one embodiment, each -R4 independently, -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β In one embodiment, each -R 4 independently -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group. In one embodiment, each -R 4 -R α -OR β or -R α -SR β In one embodiment, each -R 4 independently -R α -OR β or -R α -SR β -R β is a saccharidyl group.

[0081] In one embodiment of the first or second aspect of the invention, -R 2 , -R 3 or -R 4 At least one of the following may be independently -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β -R β is a saccharidyl group. In one embodiment, -R 2 , -R 3 or -R 4 At least one of the following may be independently -R α -OR β or -Rα -SR β -R β is a saccharidyl group.

[0082] For purposes of the present invention, a "saccharidyl group" is any group comprising at least one monosaccharide subunit, each of which may be optionally substituted and / or modified. Typically, a saccharidyl group is composed of one or more monosaccharide subunits, each of which may be optionally substituted and / or modified.

[0083] Usually, the carbon atom of a single monosaccharide subunit of each saccharidyl group is directly attached to the remainder of the compound, most typically via a single bond.

[0084] For purposes of this specification, when a first atom or group is said to be "directly bonded" to a second atom or group, it is to be understood that the first atom or group is covalently bonded to the second atom or group and that there are no intervening atom(s) or group(s). For example, in the group -(C=O)N(CH), the carbon atom of each methyl group is directly bonded to the nitrogen atom and the carbon atom of the carbonyl group is directly bonded to the nitrogen atom, but the carbon atom of the carbonyl group is not directly bonded to the carbon atoms of either methyl group.

[0085] Typically, each saccharidyl group is derived from the corresponding saccharide by replacing a hydroxyl group of the saccharide with a group defined by the remainder of the compound.

[0086] The single bond between the anomeric carbon of a monosaccharide subunit and a substituent is called a glycosidic bond. A glycosidic group is attached to the anomeric carbon of a monosaccharide subunit by a glycosidic bond. The bond between the saccharidyl group and the rest of the compound can be a glycosidic or non-glycosidic bond. Typically, the bond between the saccharidyl group and the rest of the compound is a glycosidic bond, and the saccharidyl group is a glycosyl group. When the bond between the saccharidyl group and the rest of the compound is a glycosidic bond, the glycosidic bond can be in the α or β configuration. Typically, such glycosidic bond is in the β configuration.

[0087] For purposes of the present invention, when a saccharidyl group "contains x monosaccharide subunits," this means that the saccharidyl group has x monosaccharide subunits and no more. In contrast, when a saccharidyl group "comprises x monosaccharide subunits," this means that the saccharidyl group has x or more monosaccharide subunits.

[0088] Each saccharidyl group can be independently selected from a monosaccharide, disaccharide, oligosaccharide, or polysaccharide group. As will be understood, a monosaccharide group contains a single monosaccharide subunit. Similarly, a disaccharide group contains two monosaccharide subunits. As used herein, an "oligosaccharide group" contains two to nine monosaccharide subunits. Examples of oligosaccharide groups include trisaccharide, tetrasaccharide, pentasaccharide, hexasaccharide, heptasaccharide, octasaccharide, and nonasaccharide groups. As used herein, a "polysaccharide group" contains 10 or more monosaccharide subunits (such as 10 to 50, or 10 to 30, or 10 to 20, or 10 to 15 monosaccharide subunits).

[0089] Each monosaccharide subunit within a disaccharide, oligosaccharide, or polysaccharide group can be the same or different. Each monosaccharide subunit within a disaccharide, oligosaccharide, or polysaccharide group can be linked to another monosaccharide subunit within the group via a glycosidic or non-glycosidic bond. Typically, each monosaccharide subunit within a disaccharide, oligosaccharide, or polysaccharide group is linked to another monosaccharide subunit within the group via a glycosidic bond, which can be in the α or β configuration.

[0090] Each oligosaccharidyl or polysaccharidyl group may be a linear, branched or macrocyclic oligosaccharidyl or polysaccharidyl group. Typically, each oligosaccharidyl or polysaccharidyl group is a linear or branched oligosaccharidyl or polysaccharidyl group.

[0091] In one embodiment, at least one -R β is a monosaccharide or disaccharide group.

[0092] In a further embodiment, at least one -R β is a monosaccharidyl group. For example, at least one -R β can be a glycosyl group containing a single monosaccharide subunit, where the monosaccharide subunit can be optionally substituted and / or modified. Typically, at least one -R β is a glycosyl group containing a single monosaccharide subunit, where the monosaccharide subunit can be optionally substituted. More typically, at least one -R β is a glycosyl group containing a single monosaccharide subunit, where the monosaccharide subunit is unsubstituted.

[0093] In one embodiment, at least one -R β is an aldosyl group, where the aldosyl group can be optionally substituted and / or modified. For example, at least one -R βmay be selected from a glycerosyl, aldotetrosyl (such as erythrosyl or threosyl), aldopentosyl (such as ribosyl, arabinosyl, xylosyl or lyxosyl) or aldohexosyl (such as allosyl, altrosyl, glucosyl, mannosyl, gulosyl, idosyl, galactosyl or talosyl) group, any of which may be optionally substituted and / or modified.

[0094] In another embodiment, at least one -R β is a ketosyl group, where the ketosyl group can be optionally substituted and / or modified. For example, at least one -R β may be selected from an erythrulosyl, ketopentosyl (such as ribulosyl or xylulosyl) or ketohexosyl (such as psicosyl, fructosyl, sorbosyl or tagatosyl) group, any of which may be optionally substituted and / or modified.

[0095] Each monosaccharide subunit can exist in a closed (cyclic) or open (acyclic) form. Typically, at least one -R β Each monosaccharide subunit in β can be a glycosyl group containing a single closed-ring monosaccharide subunit, where the monosaccharide subunit can be optionally substituted and / or modified. Typically, in such a scenario, at least one -R β is a pyranosyl or furanosyl group, such as an aldopyranosyl, aldofuranosyl, ketopyranosyl, or ketofuranosyl group, any of which may be optionally substituted and / or modified. More typically, at least one -R β is a pyranosyl group, such as an aldopyranosyl or ketopyranosyl group, either of which can be optionally substituted and / or modified.

[0096] In one embodiment, at least one -R βis selected from a ribopyranosyl, arabinopyranosyl, xylopyranosyl, lyxopyranosyl, allopyranosyl, altropyranosyl, glucopyranosyl, mannopyranosyl, gulopyranosyl, idopyranosyl, galactopyranosyl or talopyranosyl group, any of which may be optionally substituted and / or modified.

[0097] In a further embodiment, at least one -R β is a glucosyl group, such as a glucopyranosyl group, where the glucosyl or glucopyranosyl group may be optionally substituted and / or modified. Typically, at least one -R β is a glucosyl group, where the glucosyl group can be optionally substituted. More typically, at least one -R β is an unsubstituted glucosyl group.

[0098] Each monosaccharide subunit can be in the D-configuration or the L-configuration. Typically, each monosaccharide subunit is present in the configuration most commonly found in nature.

[0099] In one embodiment, at least one -R β is a D-glucosyl group, such as a D-glucopyranosyl group, where the D-glucosyl or D-glucopyranosyl group may be optionally substituted and / or modified. Typically, at least one -R β is a D-glucosyl group, where the D-glucosyl group can be optionally substituted. More typically, at least one -R β is an unsubstituted D-glucosyl group.

[0100] For purposes of the present invention, in the substituted monosaccharide group or monosaccharide subunit: (a) One or more hydroxyl groups of a monosaccharide group or monosaccharide subunit may each independently be -H, -F, -Cl, -Br, -I, -CF3, -CCl3, -CBr3, -CI3, -SH, -NH2, -N3, -NH=NH2, -CN, -NO2, -COOH, -R b , -OR b、-S-R b 、-R a -O-R b 、-R a -S-R b 、-SO-R b 、-SO2-R b 、-SO2-OR b 、-O-SO-R b 、-O-SO2-R b 、-O-SO2-OR b 、-NR b -SO-R b 、-NR b -SO2-R b 、-NR b -SO2-OR b 、-R a -SO-R b 、-R a -SO2-R b 、-R a -SO2-OR b 、-SO-N(R b )2、-SO2-N(R b )2、-O-SO-N(R b )2、-O-SO2-N(R b )2、-NR b -SO-N(R b )2、-NR b -SO2-N(R b )2、-R a -SO-N(R b )2、-R a -SO2-N(R b )2、-N(R b )2、-N(R b )3 + 、-R a -N(R b )2、-R a -N(R b )3 + 、-P(R b )2、-PO(R b )2、-OP(R b )2、-OPO(R b )2、-R a -P(R b )2、-R a -PO(R b )2、-OSi(R b )3、-Ra -Si(R b )3, -CO-R b , -CO-OR b , -CO-N(R b )2, -O-CO-R b , -O-CO-OR b , -O-CO-N(R b )2, -NR b -CO-R b , -NR b -CO-OR b , -NR b -CO-N(R b )2, -R a -CO-R b , -R a -CO-OR b , or -R a -CO-N(R b )2; and / or (b) one, two, or three hydrogen atoms directly attached to a carbon atom of a monosaccharide group or monosaccharide subunit are each independently -F, -Cl, -Br, -I, -CF3, -CCl3, -CBr3, -CI3, -OH, -SH, -NH2, -N3, -NH=NH2, -CN, -NO2, -COOH, -R b , -OR b , -SR b , -R a -OR b , -R a -SR b , -SO-R b , -SO2-R b , -SO2-OR b , -O-SO-R b , -O-SO2-R b , -O-SO2-OR b , -NR b -SO-R b , -NR b -SO2-R b , -NR b -SO2-OR b , -R a -SO-R b , -R a -SO2-R b , -R a -SO2-ORb , -SO-N(R b )2, -SO2-N(R b )2, -O-SO-N(R b )2, -O-SO2-N(R b )2, -NR b -SO-N(R b )2, -NR b -SO2-N(R b )2, -R a -SO-N(R b )2, -R a -SO2-N(R b )2, -N(R b )2, -N(R b )3 + , -R a -N(R b )2, -R a -N(R b )3 + , -P(R b )2, -PO(R b )2, -OP(R b )2, -OPO(R b )2, -R a -P(R b )2, -R a -PO(R b )2, -OSi(R b )3, -R a -Si(R b )3, -CO-R b , -CO-OR b , -CO-N(R b )2, -O-CO-R b , -O-CO-OR b , -O-CO-N(R b )2, -NR b -CO-R b , -NR b -CO-OR b , -NR b -CO-N(R b )2, -R a -CO-R b , -R a -CO-OR b , or -R a -CO-N(R b )2; and / or (c) one or more of the hydroxyl groups of the saccharidyl group or monosaccharide subunit, together with the hydrogen bonded to the same carbon atom as the hydroxyl group, are each independently represented by ═O, ═S, or ═NR b , or =N(R b )2 + and / or is substituted with (d) Any two hydroxyl groups of a monosaccharide group or monosaccharide subunit together form -OR c -, -SR c -, -SO-R c -, -SO2-R c -or-NR b -R c -substituted with; where: Each-R a - is independently a substituted or unsubstituted alkylene, alkenylene, or alkynylene group which optionally contains one or more heteroatoms each independently selected from O, N, and S in its carbon skeleton and which preferably contains 1 to 10 carbon atoms; Each-R b - is independently hydrogen or a substituted or unsubstituted straight-chain, branched, or cyclic alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl, or alkynylaryl group optionally containing in its carbon skeleton one or more heteroatoms each independently selected from O, N, and S and preferably containing 1 to 15 carbon atoms; Each-R c - is independently a chemical bond or a substituted or unsubstituted alkylene, alkenylene, or alkynylene group optionally containing one or more heteroatoms each independently selected from O, N, and S in its carbon skeleton and preferably containing 1 to 10 carbon atoms; However, the monosaccharide group or monosaccharide subunit has at least one, preferably at least two or at least three, -OH, -OR b , -O-SO-R b , -O-SO2-R b , -O-SO2-ORb , -O-SO-N(R b )2, -O-SO2-N(R b )2, -OP(R b )2, -OPO(R b )2, -OSi(R b )3, -O-CO-R b , -O-CO-OR b , -O-CO-N(R b )2, or -OR c - is subject to inclusion.

[0101] Typically, in substituted monosaccharide groups or monosaccharide subunits, (a) one or more of the hydroxyl groups of the saccharidyl group or monosaccharide subunits are each independently -H, -F, -CF3, -SH, -NH2, -N3, -CN, -NO2, -COOH, -R b , -OR b , -SR b , -N(R b )2, -OPO(R b )2, -OSi(R b )3, -O-CO-R b , -O-CO-OR b , -O-CO-N(R b )2, -NR b -CO-R b , -NR b -CO-OR b , or -NR b -CO-N(R b )2; and / or (b) one or two of the hydrogen atoms directly attached to a carbon atom of the monosaccharide group or monosaccharide subunit are each independently -F, -CF3, -OH, -SH, -NH2, -N3, -CN, -NO2, -COOH, -R b , -OR b , -SR b , -N(R b )2, -OPO(R b )2, -OSi(R b )3, -O-CO-R b , -O-CO-OR b , -O-CO-N(R b)2, -NR b -CO-R b , -NR b -CO-OR b , or -NR b -CO-N(R b )2; and / or (c) one hydroxyl group of the monosaccharide group or monosaccharide subunit is replaced with =0, together with the hydrogen bonded to the same carbon atom as the hydroxyl group; and / or (d) Any two hydroxyl groups of a monosaccharide group or monosaccharide subunit together form -OR c -or-NR b -R c -substituted with; where: Each-R b - is independently hydrogen or a substituted or unsubstituted straight-chain, branched, or cyclic alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl, or alkynylaryl group containing 1 to 8 carbon atoms and optionally containing in its carbon skeleton one, two, or three heteroatoms each independently selected from O and N; Each-R c - is independently a substituted or unsubstituted alkylene, alkenylene, or alkynylene group optionally containing in its carbon skeleton one, two, or three heteroatoms each independently selected from O and N, and containing from 1 to 8 carbon atoms; However, the monosaccharide group or monosaccharide subunit has at least two, preferably at least three, -OH, -OR b , -OPO(R b )2, -OSi(R b )3, -O-CO-R b , -O-CO-OR b , -O-CO-N(R b )2, or -OR c - is subject to inclusion.

[0102] In one embodiment, -R βis a saccharidyl group, and one or more hydroxyl groups of the saccharidyl group are each independently -O-CO-R b Each -R b is independently C1-C4 alkyl, preferably methyl. In one embodiment, -R β is a saccharidyl group, and all hydroxyl groups of the saccharidyl group are each independently -O-CO-R b Each -R b are independently C1-C4 alkyl, preferably methyl.

[0103] In the modified monosaccharide group or monosaccharide subunit, (a) the ring of the modified monosaccharide group or monosaccharide subunit, or what would be the ring in the closed ring form of the modified monosaccharide group or monosaccharide subunit, is partially unsaturated; and / or (b) The ring oxygen of the modified monosaccharide group or monosaccharide subunit, or what would be the ring oxygen in the closed ring form of the modified monosaccharide group or monosaccharide subunit, is replaced by -S- or -NR d -, where -R d are independently hydrogen or a substituted or unsubstituted linear, branched or cyclic alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl or alkynylaryl group, optionally containing one or more heteroatoms each independently selected from O, N and S in its carbon skeleton, and preferably containing 1 to 15 carbon atoms.

[0104] Alternatively, if the modified monosaccharide subunit forms part of a disaccharide, oligosaccharide, or polysaccharide group, -R d may be a further monosaccharide subunit or subunits forming part of a disaccharide, oligosaccharide or polysaccharide group, and such further monosaccharide subunits or subunits may optionally be substituted and / or modified.

[0105] Typically, in modified monosaccharide groups or monosaccharide subunits, (a) the ring of the modified monosaccharide group or monosaccharide subunit, or what would be the ring in the closed form of the modified monosaccharide group or monosaccharide subunit, contains a single C=C; and / or (b) The ring oxygen of the modified monosaccharide group or monosaccharide subunit, or what would be the ring oxygen in the closed ring form of the modified monosaccharide group or monosaccharide subunit, is -NR d -, where -R d are independently hydrogen or a substituted or unsubstituted, linear, branched, or cyclic alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl, or alkynylaryl group containing from 1 to 8 carbon atoms, and optionally containing in its carbon skeleton one, two, or three heteroatoms each independently selected from O and N.

[0106] Typical examples of substituted and / or modified monosaccharide subunits include those corresponding to the following: (i) Deoxysugars such as deoxyribose, fucose, fuculose, and rhamnose, in which the monosaccharidyl group or the hydroxyl group of the monosaccharide subunit is replaced by -H; (ii) amino sugars, such as glucosamine and galactosamine, in which the monosaccharide group or the hydroxyl group of the monosaccharide subunit is substituted with -NH, most typically at the 2-position; and (iii) Sugar acids containing a -COOH group, such as aldonic acids (e.g., gluconic acid), urosonic acid, uronic acids (e.g., glucuronic acid), and aldaric acids (e.g., gulanic or galactaric acid).

[0107] In one embodiment of the first or second aspect of the invention, at least one -R β is the following: [ka] is a saccharidyl group selected from:

[0108] Preferably, in the compound or complex according to the first or second aspect of the invention, at least one -R β teeth, [ka] is.

[0109] In one embodiment of the first or second aspect of the invention, -R 2 , -R 3 or -R 4 At least one of the following must be -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O)2R β (preferably -R α -OR β or -R α -SR β ) are independently selected from -R β is the following: [ka] Selected from TIFF2025539865000015.tif82159.

[0110] In one embodiment of the first or second aspect of the invention, -R 2 , -R 3 or -R 4 At least one of the following must be -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y, -R α -[R 8 ]Y, -R α -[N(R 5 )2(R 5’ )], -R α -[P(R5 )2(R 5’ )], or -R α -[R 8’ In one embodiment, -R 2 , -R 3 or -R 4 At least one of the following must be -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y, or -R α -[R 8 ]Y. In one embodiment, -R 2 , -R 3 or -R 4 At least one of the following: [ka] are independently selected from

[0111] In the first or second aspect of the present invention, each -R 5 may be the same or different. In a preferred embodiment, each -R 5 is the same.

[0112] In one embodiment of the first or second aspect of the invention, each -R 5 is independently unsubstituted or substituted with one or two substituents. In one embodiment, each -R 5 is non-substituted.

[0113] In one embodiment of the first or second aspect of the invention, -R 8 is unsubstituted or substituted with one or two substituents. In one embodiment, -R 8 is non-substituted.

[0114] In one embodiment, -R 8 is not substituted with a halo group at the 4-position of the pyridine ring. 8 is unsubstituted at the 4-position of the pyridine ring. 8 is non-substituted.

[0115] In certain preferred embodiments, the first or second aspect of the present invention provides a compound of formula (I) or a complex of formula (II): [ka] or a pharmaceutically acceptable salt thereof, wherein: -R 1 is -C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )(R 3’ ) and -R 3 is R α -OR β or -R α -SR β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl; -R 6 is as follows: (a)-C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )2, and -R 3 are each independently C1-C4 alkyl, preferably -R 6 -C(O)-OR 3 and -R 3 is C1-C4 alkyl; or (b)-C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )(R 3’ ) and -R 3 -R α -OR β or -R α -SR β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl; -R 7 is as follows: (a)-C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )2, and -R 3 are each independently C1-C4 alkyl, preferably -R 7 -C(O)-OR 3 and -R 3 is C1-C4 alkyl; or (b)-C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )(R 3’ ) and -R 3 -R α -OR β or -R α -SR β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl; -R α - is C1-C 12 alkylene groups, which may be substituted with one or more C1-C4 alkyl, C1-C4 haloalkyl or halo groups, and one or more carbon atoms in the backbone of the alkylene group may be substituted with one or more heteroatoms O or S; M 2+ is a metal cation.

[0116] In certain preferred embodiments, the first or second aspect of the present invention provides a compound of formula (I) or a complex of formula (II): [ka] or a pharmaceutically acceptable salt thereof, wherein: -R 1 is as follows: (a)-C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )2, and -R 3 are each independently -Rβ and -R β is a C1-C4 alkyl group, more preferably -R 1 is -C(O)-OR 3 and -R 3 -R β and -R β is a C1-C4 alkyl group; or (b)-C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )(R 3’ ) and -R 3 Ha-R α -OR β or -R α -SR β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl; -R 6 is -C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )(R 3’ ) and -R 3 is R α -OR β or -R α -SR β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl; -R 7 is as follows: (a)-C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )2, and -R 3 are each independently C1-C4 alkyl, preferably -R 7 -C(O)-OR 3 and -R 3 is C1-C4 alkyl; or (b)-C(O)-OR 3 , -C(O)-SR 3or -C(O)-N(R 3 )(R 3’ ) and -R 3 -R α -OR β or -R α -SR β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl; -R α - is C1-C 12 alkylene groups, which may be substituted with one or more C1-C4 alkyl, C1-C4 haloalkyl or halo groups, and one or more carbon atoms in the backbone of the alkylene group may be substituted with one or more heteroatoms O or S; M 2+ is a metal cation.

[0117] In certain preferred embodiments, the first or second aspect of the present invention provides a compound of formula (I) or a complex of formula (II): [ka] or a pharmaceutically acceptable salt thereof, wherein: -R 1 is as follows: (a)-C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )2, and -R 3 are each independently -R β and -R β is a C1-C4 alkyl group, more preferably -R 1 is -C(O)-OR 3 and -R 3 -R β and -R β is a C1-C4 alkyl group; or (b)-C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )(R3’ ) and -R 3 -R α -OR β or -R α -SR β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl; -R 6 is as follows: (a)-C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )2, and -R 3 are each independently C1-C4 alkyl, preferably -R 6 -C(O)-OR 3 and -R 3 is C1-C4 alkyl; or (b)-C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )(R 3’ ) and -R 3 -R α -OR β or -R α -SR β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl; -R 7 is -C(O)-OR 3 , -C(O)-SR 3 or -C(O)-N(R 3 )(R 3’ ) and -R 3 is R α -OR β or -R α -SR β -R β is a saccharidyl group, and -R 3’ is H or C1-C4 alkyl; -R α - is C1-C 12alkylene groups, which may be substituted with one or more C1-C4 alkyl, C1-C4 haloalkyl or halo groups, and one or more carbon atoms in the backbone of the alkylene group may be substituted with one or more heteroatoms O or S; M 2+ is a metal cation.

[0118] In certain preferred embodiments, the first or second aspect of the present invention provides a compound of formula (I) or a complex of formula (II): [ka] or a pharmaceutically acceptable salt thereof, wherein: -R 1 is -CH2OR 2 , -CH2SR 2 , -CH2S(O)R 2 , -CH2S(O)2R 2 , -CHN(R 2 )(R 2’ ), -R 2 , -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )(R 3’ ), -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )(R 3’ ) [preferably, -R 1 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )(R 3’ ), -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )(R 3’ ), more preferably selected from -R 1 is -C(O)-N(R 3 )(R 3’ ) is]; -R 2 -H, -C(O)R 4、-C(O)-OR 4 、-C(O)-SR 4 、-C(O)-N(R 4 )(R 4’ )、-C(S)-OR 4 、-C(S)-SR 4 、-C(S)-N(R 4 )(R 4’ )、-R α -H、-R β 、-R α -R β 、-R α -OH、-R α -OR β 、-R α -SH、-R α -SR β 、-R α -S(O)R β 、-R α -S(O)2R β 、-R α -NH2、-R α -NH(R β )、-R α -N(R β )2、-R α -X、-[(CH2) p Q] r -(CH2) s -[N(R 5 )3]Y、-[(CH2) p Q] r -(CH2) s -[P(R 5 )3]Y、-[(CH2) p Q] r -(CH2) s -[R 8 ]Y、-[(CH2) p Q] r -(CH2) s -[N(R 5 )2(R 5’ )]、-[(CH2) p Q] r -(CH2) s -[P(R 5 )2(R 5’ )]または-[(CH2) p Q] r -(CH2) s -[R 8’] is selected from; -R 3 and -R 4 are independently -H, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α -NH(R β ), -R α -N(R β )2, -R α -X, -[(CH2) p Q] r -(CH2) s -[N(R 5 )3]Y, -[(CH2) p Q] r -(CH2)- s -[P(R 5 )3]Y, -[(CH2) p Q] r -(CH2) s -[R 8 ]Y, -[(CH2) p Q] r -(CH2) s -[N(R 5 )2(R 5’ )], -[(CH2) p Q] r -(CH2) s -[P(R 5 )2(R 5’ )] or -[(CH2) p Q] r -(CH2) s -[R 8’ ] is selected from; -R 2 , -R 3 , and -R 4 At least one of the -[(CH2) p Q]r -(CH2) s -[N(R 5 )3]Y, -[(CH2) p Q] r -(CH2) s -[P(R 5 )3]Y, -[(CH2) p Q] r -(CH2) s -[R 8 ]Y, -[(CH2) p Q] r -(CH2) s -[N(R 5 )2(R 5’ )], -[(CH2) p Q] r -(CH2) s -[P(R 5 )2(R 5’ )] or -[(CH2) p Q] r -(CH2) s -[R 8’ ] is selected from; -R 2’ , -R 3’ , and -R 4’ are each independently selected from hydrogen or C1-C6 alkyl, preferably -R 2’ , -R 3’ , and -R 4’ are each independently selected from hydrogen or C1-C3 alkyl, more preferably -R 2’ , -R 3’ , and -R 4’ are each independently selected from hydrogen or methyl; -R α - are each independently C1-C 42 alkylene groups, which may be optionally substituted with one or more (e.g., 1, 2, 3, 4, or 5) C1-C4 alkyl, C1-C4 haloalkyl, or halo groups, and one or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) carbon atoms in the backbone of the alkylene group may be optionally substituted with a heteroatom or group independently selected from O, S, NH, or NMe; -R βare each independently a saturated or unsaturated hydrocarbyl group which may be linear or branched or is or includes a cyclic group which may be optionally substituted and which may optionally include one or more (e.g., 1, 2, 3, 4, or 5) heteroatoms N, O, S, P, or Se in its carbon skeleton; -R 5 are each independently C1-C4 alkyl, C1-C4 haloalkyl, -(CH2CH2O) n -H, -(CH2CH2O) n and selected from —CH3, phenyl, or C5-C6 heteroaryl, wherein phenyl or C5-C6 heteroaryl optionally comprises one or more (e.g., 1, 2, 3, 4, or 5) C1-C6 alkyl, C1-C6 haloalkyl, O(C1-C6 alkyl), —O(C1-C6 haloalkyl), halo, —CO2H, —CO2Z, —CO2NH2, —O—(CH2CH2O) n -H or -O-(CH2CH2O) n may be substituted with -CH3 groups; -R 5’ is C1-C4 alkyl, C1-C4 haloalkyl, -(CH2CH2O) n -H, -(CH2CH2O) n -CH3, phenyl, or C5-C6 heteroaryl, each of which is -CO2 - and the phenyl or C5-C6 heteroaryl is optionally substituted with one or more (e.g., 1, 2, 3, or 4) C1-C6 alkyl, C1-C6 haloalkyl, —O(C1-C6 alkyl), —O(C1-C6 haloalkyl), halo, —CO2H, —CO2Z, —CO2NH2, —O—(CH2CHO) n -H or -O-(CH2CH2O) n may be further substituted with -CH3 groups; -R 6 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )(R 3’ ), -C(S)-OR 3, -C(S)-SR 3 or -C(S)-N(R 3 )(R 3’ ) [preferably -R 6 is -C(O)-N(R 3 )(R 3’ ) is]; -R 7 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )(R 3’ ), -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )(R 3’ ) [preferably -R 7 is -C(O)-N(R 3 )(R 3’ ) is]; -R 8 is one or more (e.g., 1, 2, 3, 4, or 5) C1-C6 alkyl, C1-C6 haloalkyl, -O(C1-C6 alkyl), -O(C1-C6 haloalkyl), halo, -CO2H, -CO2Z, -CO2NH2, -O-(CH2CH2O) n -H or -O-(CH2CH2O) n -[NC5H5] optionally substituted with -CH3 groups; -R 8’ is -CO2 - and optionally substituted with one or more (e.g., 1, 2, 3, or 4) C-C alkyl, C-C haloalkyl, —O(C-C alkyl), —O(C-C haloalkyl), halo, —COH, —COZ, —CONH, —O—(CHCHO) n -H or -O-(CH2CH2O) n -[NC5H5] further substituted with -CH3 groups; Q is O, S, NH, or NMe [preferably Q is O]; X is a halo group; Y is a counteranion; Z is a countercation; M 2+is a metal cation; n is 1, 2, 3, 4, 5 or 6; p is 0, 1, 2, 3 or 4; r is 0, 1, 2, 3, 4, 5, or 6; s is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

[0119] In certain preferred embodiments, the first or second aspect of the present invention provides a compound of formula (I) or a complex of formula (II): [ka] or a pharmaceutically acceptable salt thereof, wherein: -R 1 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )(R 3’ ), -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )(R 3’ ) [preferably -R 1 is -C(O)-N(R 3 )(R 3’ ) is]; -R 3 are independently -H, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α -NH(R β ), -R α -N(R β )2, -R α-X, -[(CH2) p Q] r -(CH2) s -[N(R 5 )3]Y, -[(CH2) p Q] r -(CH2) s -[P(R 5 )3]Y, -[(CH2) p Q] r -(CH2) s -[R 8 ]Y, -[(CH2) p Q] r -(CH2) s -[N(R 5 )2(R 5’ )], -[(CH2) p Q] r -(CH2) s -[P(R 5 )2(R 5’ )] or -[(CH2) p Q] r -(CH2) s -[R 8’ ]; where at least one -R 3 is -[(CH2) p Q] r -(CH2) s -[N(R 5 )3]Y, -[(CH2) p Q] r -(CH2) s -[P(R 5 )3]Y, -[(CH2) p Q] r -(CH2) s -[R 8 ]Y, -[(CH2) p Q] r -(CH2) s -[N(R 5 )2(R 5’ )], -[(CH2) p Q] r -(CH2) s -[P(R 5 )2(R 5’ )] or -[(CH2) p Q] r -(CH2) s -[R8’ ] is selected from; -R 3’ is selected from hydrogen or C1-C3 alkyl, preferably -R 3’ is hydrogen or methyl]; -R α - are each independently C1-C 42 alkylene groups, which can be optionally substituted with one or more (e.g., 1, 2, 3, 4, or 5) C-C alkyl, C-C haloalkyl, or halo groups, and one or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) carbon atoms in the backbone of the alkylene group can be optionally substituted with a heteroatom or group independently selected from O, S, NH, or NMe; -R β are each independently a saturated or unsaturated hydrocarbyl group which may be linear or branched or may be or include a cyclic group which may be optionally substituted and which may optionally include one or more (e.g., 1, 2, 3, 4 or 5) heteroatoms N, O, S, P or Se in its carbon skeleton; -R 5 are each independently selected from C1-C3 alkyl or phenyl, where phenyl is optionally selected from 1-C6 alkyl, —O(C1-C6 alkyl), —CO2H, —CO2Z, —CO2NH2, —O—(CH2CH2O) n -H or -O-(CH2CH2O) n may be substituted with 1, 2, 3, 4, or 5 substituents independently selected from -CH3; -R 5’ is -CO2 - C1-C3 alkyl substituted with -CO2 - phenyl optionally substituted with C1-C6 alkyl, —O(C1-C6 alkyl), —CO2H, —CO2Z, —CO2NH2, —O—(CH2CH2O) n -H or -O-(CH2CH2O) nmay be further substituted with 1, 2, 3, or 4 substituents independently selected from -CH3; -R 6 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )(R 3’ ), -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )(R 3’ ) [preferably -R 6 is -C(O)-N(R 3 )(R 3’ ) is]; -R 7 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )(R 3’ ), -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )(R 3’ ) [preferably -R 7 is -C(O)-N(R 3 )(R 3’ ) is]; -R 8 is C1-C6 alkyl, -O(C1-C6 alkyl), -CO2H, -CO2Z, -CO2NH2, -O-(CH2CH2O) n -H or -O-(CH2CH2O) n -[NC5H5] optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from -CH3; -R 8’ is -CO2 - Substituted with C1-C6 alkyl, -O(C1-C6 alkyl), -CO2H, -CO2Z, -CO2NH2, -O-(CH2CH2O) n -H or -O-(CH2CH2O) n -[NC5H5] optionally further substituted with 1, 2, 3, or 4 substituents independently selected from -CH3; Q is O, S, NH, or NMe [preferably Q is O]; X is a halo group; Y is a counteranion; Z is a countercation; M 2+ is a metal cation; n is 1, 2, 3, 4, 5 or 6; p is 0, 1, 2, 3 or 4; r is 0, 1, 2, 3, 4, 5, or 6; s is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

[0120] In these two preferred embodiments of the previous paragraph, each -R 5 may be the same or different. Preferably, each -R 5 is the same.

[0121] In another preferred form of one embodiment of the first or second aspect of the invention, the compound is a compound of formula (IA), (IB), (IC), (ID), (IE), (IF), (IG), (IH), (IJ), (IK), (IL), (IM), (IN), (IO), (IP), (IQ), (IR), (IS), (IT), (IU) or (IV): [ka] TIFF2025539865000023.tif181159TIFF2025539865000024.tif221159TIFF2025539865000025.tif185159TIFF2025539865000026.tif85159, or a metal cation complex thereof, or a pharmaceutically acceptable salt thereof, wherein -R 1 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )(R 3’ ), -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R3 )(R 3’ ) are selected from; -R 3 are independently -H, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α -NH(R β ), -R α -N(R β )2, or -R α -X is selected from; -R 3’ is selected from hydrogen or C1-C3 alkyl (preferably hydrogen or methyl); -R 6 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )(R 3’ ), -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )(R 3’ ) are selected from; -R 7 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )(R 3’ ), -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )(R 3’ ) are selected from; -R α - are each independently C1-C 12alkylene groups, which may be optionally substituted with one or more (e.g., 1, 2, 3, 4, or 5) C1-C4 alkyl, C1-C4 haloalkyl, or halo groups, and one or more (e.g., 1, 2, 3, 4, 5, or 6) carbon atoms in the backbone of the alkylene group may be optionally replaced with a heteroatom or group independently selected from O, S, NH, or NMe; -R β are each independently a saturated or unsaturated hydrocarbyl group which may be linear or branched or may be or include a cyclic group which may be optionally substituted and which may optionally include one or more (e.g., 1, 2, 3, 4 or 5) heteroatoms N, O, S, P or Se in its carbon skeleton; -R δ is selected from C1-C3 alkyl; -R ε is C1-C6 alkyl, -O(C1-C6 alkyl), -CO2H, -CO2Z, -CO2NH2, -O-(CH2CH2O) n -H or -O-(CH2CH2O) n - selected from CH3; X is a halo group; Y is a counteranion; Z is a countercation; n is 1, 2, 3 or 4; p is 0, 1, 2, 3 or 4; r is 0, 1, 2, 3, 4, 5, or 6; s is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; t is 0, 1, 2, 3, 4 or 5; u is 0, 1, 2, 3 and 4.

[0122] The compounds of formula (IA), (IB), (IC), (ID), (IE), (IF), (IG), (IH), (IJ), (IK), (IL), (IM), (IN), (IO), (IP), (IQ), (IR), (IS), (IT), (IU), (IV) and complexes and salts thereof according to the first and second aspects of the present invention comprise a moiety -[(CH2) p O] r -(CH2) s -, wherein p is 0, 1, 2, 3 or 4; r is 0, 1, 2, 3, 4, 5, or 6; s is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

[0123] In one embodiment, p is 2, 3, or 4, r is 1, and s is 2, 3, or 4. In a preferred embodiment, 3-[(CH) p O] r -(CH2) s p is 3, r is 1, and s is 3, so that - is -(CH2)3-O-(CH2)3-.

[0124] In another embodiment, p is 2 or 3, r is 2 or 3, and s is 2 or 3. In a preferred embodiment, -[(CH) p O] r -(CH2) s p is 2, r is 2, and s is 2 so that - is -(CH2CH2O)2-(CH2)2-.

[0125] In yet another embodiment, -[(CH) p O] r -(CH2) s -ga-(CH2) 1-12 -, r is 0, and s is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

[0126] Preferably, in the compound or complex according to the first or second aspect of the invention, the compound or complex comprises: [ka] , wherein Y is a counter anion and q is 0, 1, 2, 3, or 4 (preferably, q is 1). or a metal cation complex thereof, or a pharmaceutically acceptable salt thereof.

[0127] In certain preferred embodiments, the first or second aspect of the present invention provides a compound of formula (I) or a complex of formula (II): [ka] or a pharmaceutically acceptable salt thereof, wherein: -R 1 is -CO2H or -CO2R 13 Selected from; -R 6 is -CO2H or -CO2R 13 Selected from; -R 7 is -C(O)-R 14 -R 15 Selected from; -R 13 is selected from C1-C3 alkyl; -R 14 is selected from NMe, O or S; -R 15 is C1-C 20 alkyl, wherein one or more carbon atoms of the alkyl group can be optionally substituted with a heteroatom or group independently selected from O, S, NH, or NMe, and the alkyl group can be optionally substituted with one or more (e.g., 1, 2, 3, 4, 5, 6, 7, or 8) —OH or —NH groups; M 2+ is a metal cation; However, -R 7 is not a -CO2Me group or a -CO2Et group.

[0128] In one embodiment of this particular preferred embodiment of the first or second aspect of the invention, the compound of formula (I) or the complex of formula (II) is [Table 1] or any enantiomer thereof; or a racemic mixture of either; Or a salt of any of them, not.

[0129] In another embodiment of this particularly preferred embodiment of the first or second aspect of the invention, M 2+ is as defined in any of the embodiments described above for the first aspect of the invention.

[0130] In one embodiment of this particularly preferred embodiment, -R 1 is -CO2H.

[0131] In another embodiment of this particularly preferred embodiment, -R 1 -CO2R 13 In one embodiment, -R 13 is methyl, ethyl, or propyl. Preferably, -R 13 is methyl or ethyl. Preferably, -R 13 is methyl.

[0132] In one embodiment of this particularly preferred embodiment, -R 6 is -CO2H.

[0133] In another embodiment of this particularly preferred embodiment, -R 6 -CO2R 13 In one embodiment, -R 13 is methyl, ethyl, or propyl. Preferably, -R 13 is methyl or ethyl. Preferably, -R 13 is methyl.

[0134] In one embodiment of this particularly preferred embodiment, -R 7 is -C(O)-R 14 -(CH2) x -H, -C(O)-R 14-(CH2) x -OH, -C(O)-R 14 -(CH2CH2O) y -Me or -C(O)-R 14 -(CH2CH2O) y -H, where x is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, and y is 0, 1, 2, 3, 4, 5 or 6. Preferably, -R 7 is -C(O)-R 14 -(CH2) x -H or -C(O)-R 14 -(CH2CH2O) y -Me. In one embodiment, x is 1, 2, 3, 4, 5 or 6. Preferably, x is 3, 4 or 5. Preferably, x is 4. In one embodiment, y is 1, 2, 3, 4, 5 or 6. Preferably, y is 1, 2, 3 or 4. Preferably, y is 1.

[0135] In one embodiment, -R 14 - is NMe or O. Preferably, -R 14 - is NMe.

[0136] In another particularly preferred embodiment, the first or second aspect of the invention provides a compound of formula (I) or a complex of formula (II): [ka] or a pharmaceutically acceptable salt thereof, wherein: -R 1 is -CO2H or -CO2R 13 Selected from; -R 6 is -CO2H or -CO2R 13 Selected from; -R 7 is -C(O)-R 14 -R 15 Selected from; -R 13 is selected from C1-C3 alkyl; -R 14- is selected from NH, NMe, O or S; -R 15 is C4-C 20 alkyl, wherein one or more carbon atoms of the alkyl group can be optionally substituted with a heteroatom or group independently selected from O, S, NH, or NMe, and the alkyl group can be optionally substituted with one or more (e.g., 1, 2, 3, 4, 5, 6, 7, or 8) —OH or —NH groups; M 2+ is a metal cation; However, -R 7 is not a -CO2Me group or a -CO2Et group.

[0137] In one embodiment of this particular preferred embodiment of the first or second aspect of the invention, the compound of formula (I) or the complex of formula (II) is [Table 2] TIFF2025539865000032.tif19159 or any of their enantiomers; or a racemic mixture of either; Or a salt of any of them, not.

[0138] In another embodiment of this particularly preferred embodiment of the first or second aspect of the invention, M 2+ is as defined in any of the embodiments described above for the first aspect of the invention.

[0139] In one embodiment of this particularly preferred embodiment, -R 1 is -CO2H.

[0140] In another embodiment of this particularly preferred embodiment, -R 1 -CO2R 13 In one embodiment, -R 13 is methyl, ethyl, or propyl. Preferably, -R 13 is methyl or ethyl. Preferably, -R 13is methyl.

[0141] In one embodiment of this particularly preferred embodiment, -R 6 is -CO2H.

[0142] In another embodiment of this particularly preferred embodiment, -R 6 -CO2R 13 In one embodiment, -R 13 is methyl, ethyl, or propyl. Preferably, -R 13 is methyl or ethyl. Preferably, -R 13 is methyl.

[0143] In one embodiment of this particularly preferred embodiment, -R 7 is -C(O)-R 14 -(CH2) x -H, -C(O)-R 14 -(CH2) x -OH, -C(O)-R 14 -(CH2CH2O) y -Me or -C(O)-R 14 -(CH2CH2O) y’ -H, where x is 4, 5, 6, 7, 8, 9, 10, 11 or 12, and y' is 2, 3, 4, 5 or 6. Preferably, -R 7 is -C(O)-R 14 -(CH2) x -H or -C(O)-R 14 -(CH2CH2O) y -Me. In one embodiment, x is 4, 5 or 6. Preferably, x is 4 or 5. Preferably, x is 4. In one embodiment, y is 1, 2, 3, 4, 5 or 6. Preferably, y is 1, 2, 3 or 4. Preferably, y is 1. In one embodiment, y' is 2, 3, 4, 5 or 6. Preferably, y' is 2, 3 or 4.

[0144] In one embodiment, -R 14 - is NH, NMe or O. Preferably, -R 14- is NH or NMe. Preferably, -R 14 - is NMe.

[0145] In another particularly preferred embodiment, the first or second aspect of the invention provides a compound of formula (I) or a complex of formula (II): [ka] or a pharmaceutically acceptable salt thereof, wherein: -R 1 is -CH2OR 2 , -CH2SR 2 , -CH2S(O)R 2 , -CH2S(O)2R 2 , -CHN(R 2 )2, -R 2 , -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2 is selected; -R 2 are each independently H, -C(O)R 4 , -C(O)-OR 4 , -C(O)-SR 4 , -C(O)-N(R 4 )2, -C(S)-OR 4 , -C(S)-SR 4 , -C(S)-N(R 4 )2, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α-NH(R β ), -R α -N(R β )2, -R α -X, -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y, -R α -[R 8 ]Y, -R α -[N(R 5 )2(R 5’ )], -R α -[P(R 5 )2(R 5’ )] or -R α -[R 8’ ] is selected from; -R 3 and -R 4 are independently -H, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α -NH(R β ), -R α -N(R β )2, -R α -X, -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y, -R α -[R 8 ]Y, -R α -[N(R 5 )2(R 5’ )], -R α -[P(R 5 )2(R 5’ )] or R α -[R 8’ ] is selected from; -R α - are each independently C1-C 42 alkylene groups, which may be optionally substituted with one or more C1-C4 alkyl, C1-C4 haloalkyl, or halo groups, and one or more backbone carbon atoms of the alkylene group may be optionally replaced by a heteroatom or group independently selected from O, S, NH, or NMe; -R β are each independently a saturated or unsaturated hydrocarbyl group which may be linear or branched or may be or contain a cyclic group which may be optionally substituted and which may optionally include one or more heteroatoms N, O, S, P or Se in its carbon skeleton; -R 5 are each independently C1-C4 alkyl, C1-C4 haloalkyl, -(CH2CH2O) n -H, -(CH2CH2O) n and —CH3, phenyl, or C5-C6 heteroaryl, wherein phenyl or C5-C6 heteroaryl optionally comprises one or more of C1-C6 alkyl, C1-C6 haloalkyl, —O(C1-C6 alkyl), —O(C1-C6 haloalkyl), halo, —CO2H, —CO2Z, —CO2NH2, —O—(CH2CH2O) n -H or -O-(CH2CH2O) n may be substituted with -CH3 groups; -R 5’ is C1-C4 alkyl, C1-C4 haloalkyl, -(CH2CH2O) n -H, -(CH2CH2O) n -CH3, phenyl, or C5-C6 heteroaryl, each of which is -CO2 - and the phenyl or C5-C6 heteroaryl is optionally substituted with one or more of C1-C6 alkyl, C1-C6 haloalkyl, —O(C1-C6 alkyl), —O(C1-C6 haloalkyl), halo, —CO2H, —CO2Z, —CO2NH2, —O—(CH2CH2O) n -H or -O-(CH2CH2O)n may be further substituted with -CH3 groups; -R 6 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2 is selected; -R 7 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2 is selected; -R 8 is one or more of C1-C6 alkyl, C1-C6 haloalkyl, -O(C1-C6 alkyl), -O(C1-C6 haloalkyl), halo, -CO2H, -CO2Z, -CO2NH2, -O-(CH2CH2O) n -H or -O-(CH2CH2O) n -[NC5H5] optionally substituted with -CH3 groups; -R 8’ is -CO2 - and substituted with one or more of C1-C6 alkyl, C1-C6 haloalkyl, -O(C1-C6 alkyl), -O(C1-C6 haloalkyl), halo, -CO2H, -CO2Z, -CO2NH2, -O-(CH2CH2O) n -H or -O-(CH2CH2O) n -[NC5H5] optionally further substituted with -CH3 groups; n is 1, 2, 3, 4, 5 or 6; X is a halo group; Y is a counter anion; Z is a counter cation; and M 2+ is a metal cation; However, -R 1 , -R 6 , and -R 7At least one of the α -[R 8 ]Y or -R α -[R 8’ ] is required.

[0146] In another embodiment of this particularly preferred embodiment of the first or second aspect of the invention, -R 1 , -R 2 , -R 3 , -R 4 , -R 5 , -R 5’ , -R 6 , -R 7 , -R 8 , -R 8’ , -R α -, -R β , n, X, Y, Z and M 2+ is as defined in any of the embodiments described above for the first aspect of the invention.

[0147] In another particularly preferred embodiment, the first or second aspect of the invention provides a compound of formula (I) or a complex of formula (II): [ka] or a pharmaceutically acceptable salt thereof, wherein: -R 1 is -CH2OR 2 , -CH2SR 2 , -CH2S(O)R 2 , -CH2S(O)2R 2 , -CHN(R 2 )2, -R 2 , -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2 is selected; -R 2 are each independently H, -C(O)R 4 , -C(O)-OR 4, -C(O)-SR 4 , -C(O)-N(R 4 )2, -C(S)-OR 4 , -C(S)-SR 4 , -C(S)-N(R 4 )2, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α -NH(R β ), -R α -N(R β )2, -R α -X, -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y, -R α -[R 8 ]Y, -R α -[N(R 5 )2(R 5’ )], -R α -[P(R 5 )2(R 5’ )] or -R α -[R 8’ ] is selected from; -R 3 and -R 4 are independently -H, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α-S(O)2R β , -R α -NH2, -R α -NH(R β ), -R α -N(R β )2, -R α -X, -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y, -R α -[R 8 ]Y, -R α -[N(R 5 )2(R 5’ )], -R α -[P(R 5 )2(R 5’ )] or R α -[R 8’ ] is selected from; -R α - are each independently C1-C 42 alkylene groups, which may be optionally substituted with one or more C1-C4 alkyl, C1-C4 haloalkyl, or halo groups, and one or more backbone carbon atoms of the alkylene group may be optionally replaced by a heteroatom or group independently selected from O, S, NH, or NMe; -R β are each independently a saturated or unsaturated hydrocarbyl group which may be linear or branched or may be or contain a cyclic group which may be optionally substituted and which may optionally include one or more heteroatoms N, O, S, P or Se in its carbon skeleton; -R 5 are each independently C1-C4 alkyl, C1-C4 haloalkyl, -(CH2CH2O) n -H, -(CH2CH2O) nand —CH3, phenyl, or C5-C6 heteroaryl, wherein phenyl or C5-C6 heteroaryl optionally comprises one or more of C1-C6 alkyl, C1-C6 haloalkyl, —O(C1-C6 alkyl), —O(C1-C6 haloalkyl), halo, —CO2H, —CO2Z, —CO2NH2, —O—(CH2CH2O) n -H or -O-(CH2CH2O) n may be substituted with -CH3 groups; -R 5’ is C1-C4 alkyl, C1-C4 haloalkyl, -(CH2CH2O) n -H, -(CH2CH2O) n -CH3, phenyl, or C5-C6 heteroaryl, each of which is -CO2 - and the phenyl or C5-C6 heteroaryl is optionally substituted with one or more of C1-C6 alkyl, C1-C6 haloalkyl, —O(C1-C6 alkyl), —O(C1-C6 haloalkyl), halo, —CO2H, —CO2Z, —CO2NH2, —O—(CH2CH2O) n -H or -O-(CH2CH2O) n may be further substituted with -CH3 groups; -R 6 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2 is selected; -R 7 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2 is selected; -R 8is one or more of C1-C6 alkyl, C1-C6 haloalkyl, -O(C1-C6 alkyl), -O(C1-C6 haloalkyl), halo, -CO2H, -CO2Z, -CO2NH2, -O-(CH2CH2O) n -H or -O-(CH2CH2O) n -[NC5H5] optionally substituted with -CH3 groups; -R 8’ is -CO2 - and substituted with one or more of C1-C6 alkyl, C1-C6 haloalkyl, -O(C1-C6 alkyl), -O(C1-C6 haloalkyl), halo, -CO2H, -CO2Z, -CO2NH2, -O-(CH2CH2O) n -H or -O-(CH2CH2O) n -[NC5H5] optionally further substituted with -CH3 groups; n is 1, 2, 3, 4, 5 or 6; X is a halo group; Y is a counter anion; Z is a counter cation; and M 2+ is a metal cation; However, -R 1 , -R 6 and -R 7 At least one of the 14 -[(CH2) p O)] r -(CH2) s -R 14 -R 16 wherein: Each-R 14 - is independently selected from NH, NMe, O, or S; -R 16 is a saccharidyl group; p is 1, 2, 3 or 4; r is 0, 1, 2, 3, 4, 5, or 6; s is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

[0148] In another embodiment of this particularly preferred embodiment of the first or second aspect of the invention, -R 1 , -R 2 , -R 3 , -R 4 , -R 5 , -R 5’ , -R 6 , -R 7 , -R 8 , -R 8’ , -R α -, -R β , n, X, Y, Z, M 2+ and the saccharidyl group is as defined in any of the embodiments set out above for the first aspect of the invention.

[0149] In one embodiment of this particularly preferred embodiment, -R 1 , -R 6 and -R 7 At least one of the 14 -(CH2) s -R 14 -R 16 wherein s is 1, 2, 3, 4, 5 or 6. Preferably, s is 2, 3, 4 or 5. Preferably, s is 3.

[0150] In another embodiment of this particularly preferred embodiment, -R 1 , -R 6 and -R 7 At least one of the 14 -(CH2)3-O-(CH2)3-R 14 -R 16 Includes:

[0151] In another embodiment of this particularly preferred embodiment, -R 1 , -R 6 and -R 7 At least one of the 14 -(CH2CH2O)2-(CH2)2-R 14 -R 16 Includes:

[0152] In another particularly preferred embodiment, the first or second aspect of the invention provides a compound of formula (I) or a complex of formula (II): [ka] or a pharmaceutically acceptable salt thereof, wherein: -R 1 is -CH2OR 2 , -CH2SR 2 , -CH2S(O)R 2 , -CH2S(O)2R 2 , -CHN(R 2 )2, -R 2 , -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2 is selected; -R 2 are each independently H, -C(O)R 4 , -C(O)-OR 4 , -C(O)-SR 4 , -C(O)-N(R 4 )2, -C(S)-OR 4 , -C(S)-SR 4 , -C(S)-N(R 4 )2, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α -NH(R β ), -R α -N(R β )2, -R α -X, -Rα -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y, -R α -[R 8 ]Y, -R α -[N(R 5 )2(R 5’ )], -R α -[P(R 5 )2(R 5’ )] or -R α -[R 8’ ] is selected from; -R 3 and -R 4 are independently -H, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α -NH(R β ), -R α -N(R β )2, -R α -X, -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y, -R α -[R 8 ]Y, -R α -[N(R 5 )2(R 5’ )], -R α -[P(R 5 )2(R 5’ )] or R α -[R 8’ ] is selected from; -R α - are each independently C1-C 42alkylene groups, which may be optionally substituted with one or more C1-C4 alkyl, C1-C4 haloalkyl, or halo groups, and one or more backbone carbon atoms of the alkylene group may be optionally replaced by a heteroatom or group independently selected from O, S, NH, or NMe; -R β are each independently a saturated or unsaturated hydrocarbyl group which may be linear or branched or may be or contain a cyclic group which may be optionally substituted and which may optionally include one or more heteroatoms N, O, S, P or Se in its carbon skeleton; -R 5 are each independently C1-C4 alkyl, C1-C4 haloalkyl, -(CH2CH2O) n -H, -(CH2CH2O) n and —CH3, phenyl, or C5-C6 heteroaryl, wherein phenyl or C5-C6 heteroaryl optionally comprises one or more of C1-C6 alkyl, C1-C6 haloalkyl, —O(C1-C6 alkyl), —O(C1-C6 haloalkyl), halo, —CO2H, —CO2Z, —CO2NH2, —O—(CH2CH2O) n -H or -O-(CH2CH2O) n may be substituted with -CH3 groups; -R 5’ is C1-C4 alkyl, C1-C4 haloalkyl, -(CH2CH2O) n -H, -(CH2CH2O) n -CH3, phenyl, or C5-C6 heteroaryl, each of which is -CO2 - and the phenyl or C5-C6 heteroaryl is optionally substituted with one or more of C1-C6 alkyl, C1-C6 haloalkyl, —O(C1-C6 alkyl), —O(C1-C6 haloalkyl), halo, —CO2H, —CO2Z, —CO2NH2, —O—(CH2CH2O) n -H or -O-(CH2CH2O) n may be further substituted with -CH3 groups; -R 6is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2 is selected; -R 7 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2 is selected; -R 8 is one or more of C1-C6 alkyl, C1-C6 haloalkyl, -O(C1-C6 alkyl), -O(C1-C6 haloalkyl), halo, -CO2H, -CO2Z, -CO2NH2, -O-(CH2CH2O) n -H or -O-(CH2CH2O) n -[NC5H5] optionally substituted with -CH3 groups; -R 8’ is -CO2 - and substituted with one or more of C1-C6 alkyl, C1-C6 haloalkyl, -O(C1-C6 alkyl), -O(C1-C6 haloalkyl), halo, -CO2H, -CO2Z, -CO2NH2, -O-(CH2CH2O) n -H or -O-(CH2CH2O) n -[NC5H5] optionally further substituted with -CH3 groups; n is 1, 2, 3, 4, 5 or 6; X is a halo group; Y is a counter anion; Z is a counter cation; and M 2+ is a metal cation; However, -R 1 , -R 6 and -R 7 At least one of the 14 -[(CH2) p -R14 ] r -(CH2) s -R 17 wherein: Each-R 14 - is independently selected from NH, NMe, O, or S; -R 17 is -[P(R 5 )3]Y or -[P(R 5 )2(R 5’ )] and; p is 1, 2, 3 or 4; r is 0, 1, 2, 3, 4, 5, or 6; s is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

[0153] In another embodiment of this particularly preferred embodiment of the first or second aspect of the invention, -R 1 , -R 2 , -R 3 , -R 4 , -R 5 , -R 5’ , -R 6 , -R 7 , -R 8 , -R 8’ , -R α -, -R β , n, X, Y, Z and M 2+ is as defined in any of the embodiments described above for the first aspect of the invention.

[0154] In one embodiment of this particularly preferred embodiment, -R 1 , -R 6 and -R 7 At least one of the 14 -(CH2) s -R 17 wherein s is 1, 2, 3, 4, 5 or 6. Preferably, s is 2, 3, 4 or 5. Preferably, s is 3.

[0155] In another embodiment of this particularly preferred embodiment, -R 1 , -R 6 and -R7 At least one of the 14 -(CH2)3-O-(CH2)3-R 17 Includes:

[0156] In another embodiment of this particularly preferred embodiment, -R 1 , -R 6 and -R 7 At least one of the 14 -(CH2CH2O)2-(CH2)2-R 17 Includes:

[0157] In one embodiment of this particularly preferred embodiment, -R 17 is -PPh3 + Cl - or -PPh3 + Br - is.

[0158] In another particularly preferred embodiment, the first or second aspect of the invention provides a compound of formula (I) or a complex of formula (II): [ka] or a pharmaceutically acceptable salt thereof, wherein: -R 1 is -CH2OR 2 , -CH2SR 2 , -CH2S(O)R 2 , -CH2S(O)2R 2 , -CHN(R 2 )2, -R 2 , -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2 is selected; -R 2 are each independently H, -C(O)R 4 , -C(O)-OR 4 , -C(O)-SR 4 , -C(O)-N(R4 )2, -C(S)-OR 4 , -C(S)-SR 4 , -C(S)-N(R 4 )2, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α -NH(R β ), -R α -N(R β )2, -R α -X, -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y, -R α -[R 8 ]Y, -R α -[N(R 5 )2(R 5’ )], -R α -[P(R 5 )2(R 5’ )] or -R α -[R 8’ ] is selected from; -R 3 and -R 4 are independently -H, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α-NH2, -R α -NH(R β ), -R α -N(R β )2, -R α -X, -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y, -R α -[R 8 ]Y, -R α -[N(R 5 )2(R 5’ )], -R α -[P(R 5 )2(R 5’ )] or R α -[R 8’ ] is selected from; -R α - are each independently C1-C 42 alkylene groups, which may be optionally substituted with one or more C1-C4 alkyl, C1-C4 haloalkyl, or halo groups, and one or more backbone carbon atoms of the alkylene group may be optionally replaced by a heteroatom or group independently selected from O, S, NH, or NMe; -R β are each independently a saturated or unsaturated hydrocarbyl group which may be linear or branched or may be or contain a cyclic group which may be optionally substituted and which may optionally include one or more heteroatoms N, O, S, P or Se in its carbon skeleton; -R 5 are each independently C1-C4 alkyl, C1-C4 haloalkyl, -(CH2CH2O) n -H, -(CH2CH2O) n and —CH3, phenyl, or C5-C6 heteroaryl, wherein phenyl or C5-C6 heteroaryl optionally comprises one or more of C1-C6 alkyl, C1-C6 haloalkyl, —O(C1-C6 alkyl), —O(C1-C6 haloalkyl), halo, —CO2H, —CO2Z, —CO2NH2, —O—(CH2CH2O) n-H or -O-(CH2CH2O) n may be substituted with -CH3 groups; -R 5’ is C1-C4 alkyl, C1-C4 haloalkyl, -(CH2CH2O) n -H, -(CH2CH2O) n -CH3, phenyl, or C5-C6 heteroaryl, each of which is -CO2 - and the phenyl or C5-C6 heteroaryl is optionally substituted with one or more of C1-C6 alkyl, C1-C6 haloalkyl, —O(C1-C6 alkyl), —O(C1-C6 haloalkyl), halo, —CO2H, —CO2Z, —CO2NH2, —O—(CH2CH2O) n -H or -O-(CH2CH2O) n may be further substituted with -CH3 groups; -R 6 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2 is selected; -R 7 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2 is selected; -R 8 is one or more of C1-C6 alkyl, C1-C6 haloalkyl, -O(C1-C6 alkyl), -O(C1-C6 haloalkyl), halo, -CO2H, -CO2Z, -CO2NH2, -O-(CH2CH2O) n -H or -O-(CH2CH2O) n -[NC5H5] optionally substituted with -CH3 groups; -R 8’ is -CO2 -and substituted with one or more of C1-C6 alkyl, C1-C6 haloalkyl, -O(C1-C6 alkyl), -O(C1-C6 haloalkyl), halo, -CO2H, -CO2Z, -CO2NH2, -O-(CH2CH2O) n -H or -O-(CH2CH2O) n -[NC5H5] optionally further substituted with -CH3 groups; n is 1, 2, 3, 4, 5 or 6; X is a halo group; Y is a counter anion; Z is a counter cation; and M 2+ is a metal cation; However, -R 1 , -R 6 and -R 7 At least one of the (i)-R 14 -[(CH2) p -R 14 ] r -(CH2) s -R 18 [In the formula, Each-R 14 - is independently selected from NH, NMe, O, or S; -R 18 is -[N(R 5 )3]Y or -[N(R 5 )2(R 5’ )] and; p is 1, 2, 3 or 4; r is 2, 3, 4, 5 or 6; s is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12] or (ii)-R 14 -(CH2) s -R 18 [In the formula, -R 14 is selected from NH, NMe, O or S; -R 18 is -[N(R 5 )3]Y or -[N(R 5 )2(R 5’ )] and; s is 4, 5, 6, 7, 8, 9, 10, 11 or 12].

[0159] In another embodiment of this particularly preferred embodiment of the first or second aspect of the invention, -R 1 , -R 2 , -R 3 , -R 4 , -R 5 , -R 5’ , -R 6 , -R 7 , -R 8 , -R 8’ , -R α -, -R β , n, X, Y, Z and M 2+ is as defined in any of the embodiments described above for the first aspect of the invention.

[0160] In one embodiment of this particularly preferred embodiment of the first or second aspect of the invention, -R 1 , -R 6 and -R 7 At least one of the 14 -[(CH2) p -R 14 ] r -(CH2) s -R 18 wherein p is 2, 3, or 4; r is 2, 3, 4, 5, or 6; and s is 2, 3, 4, 5, or 6.

[0161] In another embodiment of this particularly preferred embodiment of the first or second aspect of the invention, -R 1 , -R 6 and -R 7 At least one of the 14 -(CH2) s -R 18 wherein s is 4, 5 or 6.

[0162] In one embodiment of this particularly preferred embodiment, -R 18 is -NMe3 + Cl -or -NMe3 + Br - is.

[0163] In another particularly preferred embodiment, the first or second aspect of the invention provides a compound of formula (I) or a complex of formula (II): [ka] or a pharmaceutically acceptable salt thereof, wherein: -R 1 is -CH2OR 2 , -CH2SR 2 , -CH2S(O)R 2 , -CH2S(O)2R 2 , -CHN(R 2 )2, -R 2 , -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2 is selected; -R 2 are each independently H, -C(O)R 4 , -C(O)-OR 4 , -C(O)-SR 4 , -C(O)-N(R 4 )2, -C(S)-OR 4 , -C(S)-SR 4 , -C(S)-N(R 4 )2, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α-NH(R β ), -R α -N(R β )2, -R α -X, -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y, -R α -[R 8 ]Y, -R α -[N(R 5 )2(R 5’ )], -R α -[P(R 5 )2(R 5’ )] or -R α -[R 8’ ] is selected from; -R 3 and -R 4 are independently -H, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α -NH(R β ), -R α -N(R β )2, -R α -X, -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y, -R α -[R 8 ]Y, -R α -[N(R 5 )2(R 5’ )], -R α -[P(R 5 )2(R 5’ )] or R α -[R 8’ ] is selected from; -R α - are each independently C1-C 42 alkylene groups, which may be optionally substituted with one or more C1-C4 alkyl, C1-C4 haloalkyl, or halo groups, and one or more backbone carbon atoms of the alkylene group may be optionally replaced by a heteroatom or group independently selected from O, S, NH, or NMe; -R β are each independently a saturated or unsaturated hydrocarbyl group which may be linear or branched or may be or contain a cyclic group which may be optionally substituted and which may optionally include one or more heteroatoms N, O, S, P or Se in its carbon skeleton; -R 5 are each independently C1-C4 alkyl, C1-C4 haloalkyl, -(CH2CH2O) n -H, -(CH2CH2O) n and —CH3, phenyl, or C5-C6 heteroaryl, wherein phenyl or C5-C6 heteroaryl optionally comprises one or more of C1-C6 alkyl, C1-C6 haloalkyl, —O(C1-C6 alkyl), —O(C1-C6 haloalkyl), halo, —CO2H, —CO2Z, —CO2NH2, —O—(CH2CH2O) n -H or -O-(CH2CH2O) n may be substituted with -CH3 groups; -R 5’ is C1-C4 alkyl, C1-C4 haloalkyl, -(CH2CH2O) n -H, -(CH2CH2O) n -CH3, phenyl, or C5-C6 heteroaryl, each of which is -CO2 - and the phenyl or C5-C6 heteroaryl is optionally substituted with one or more of C1-C6 alkyl, C1-C6 haloalkyl, —O(C1-C6 alkyl), —O(C1-C6 haloalkyl), halo, —CO2H, —CO2Z, —CO2NH2, —O—(CH2CH2O) n -H or -O-(CH2CH2O)n may be further substituted with -CH3 groups; -R 6 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2 is selected; -R 7 is -C(O)-OR 19 Selected from; -R 8 is one or more of C1-C6 alkyl, C1-C6 haloalkyl, -O(C1-C6 alkyl), -O(C1-C6 haloalkyl), halo, -CO2H, -CO2Z, -CO2NH2, -O-(CH2CH2O) n -H or -O-(CH2CH2O) n -[NC5H5] optionally substituted with -CH3 groups; -R 8’ is -CO2 - and substituted with one or more of C1-C6 alkyl, C1-C6 haloalkyl, -O(C1-C6 alkyl), -O(C1-C6 haloalkyl), halo, -CO2H, -CO2Z, -CO2NH2, -O-(CH2CH2O) n -H or -O-(CH2CH2O) n -[NC5H5] optionally further substituted with -CH3 groups; -R 19 is C3-C6 alkyl; n is 1, 2, 3, 4, 5 or 6; X is a halo group; Y is a counter anion; Z is a counter cation; and M 2+ is a metal cation.

[0164] In one embodiment of this particular preferred embodiment of the first or second aspect of the invention, the compound of formula (I) or the complex of formula (II) is [Table 3] or any enantiomer thereof; or a racemic mixture of either; Or a salt of any of them, not.

[0165] In another embodiment of this particularly preferred embodiment of the first or second aspect of the invention, -R 1 , -R 2 , -R 3 , -R 4 , -R 5 , -R 5’ , -R 6 , -R 8 , -R 8’ , -R α -, -R β , n, X, Y, Z and M 2+ is as defined in any of the embodiments described above for the first aspect of the invention.

[0166] In one embodiment of this particularly preferred embodiment of the first or second aspect of the invention, -R 19 is propyl, butyl, pentyl or hexyl.

[0167] In another particularly preferred embodiment, the first or second aspect of the invention provides a compound of formula (I) or a complex of formula (II): [ka] or a pharmaceutically acceptable salt thereof, wherein: -R 1 is -CH2OR 2 , -CH2SR 2 , -CH2S(O)R 2 , -CH2S(O)2R 2 , -CHN(R 2 )2, -R 2 , -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3or -C(S)-N(R 3 )2 is selected; -R 2 are each independently H, -C(O)R 4 , -C(O)-OR 4 , -C(O)-SR 4 , -C(O)-N(R 4 )2, -C(S)-OR 4 , -C(S)-SR 4 , -C(S)-N(R 4 )2, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α -NH(R β ), -R α -N(R β )2, -R α -X, -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y, -R α -[R 8 ]Y, -R α -[N(R 5 )2(R 5’ )], -R α -[P(R 5 )2(R 5’ )] or -R α -[R 8’ ] is selected from; -R 3 and -R 4 are independently -H, -R α -H, -R β , -R α -R β , -R α -OH, -R α -ORβ , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O)2R β , -R α -NH2, -R α -NH(R β ), -R α -N(R β )2, -R α -X, -R α -[N(R 5 )3]Y, -R α -[P(R 5 )3]Y, -R α -[R 8 ]Y, -R α -[N(R 5 )2(R 5’ )], -R α -[P(R 5 )2(R 5’ )] or R α -[R 8’ ] is selected from; -R α - are each independently C1-C 42 alkylene groups, which may be optionally substituted with one or more C1-C4 alkyl, C1-C4 haloalkyl, or halo groups, and one or more backbone carbon atoms of the alkylene group may be optionally replaced by a heteroatom or group independently selected from O, S, NH, or NMe; -R β are each independently a saturated or unsaturated hydrocarbyl group which may be linear or branched or may be or contain a cyclic group which may be optionally substituted and which may optionally include one or more heteroatoms N, O, S, P or Se in its carbon skeleton; -R 5 are each independently C1-C4 alkyl, C1-C4 haloalkyl, -(CH2CH2O) n -H, -(CH2CH2O) nand —CH3, phenyl, or C5-C6 heteroaryl, wherein phenyl or C5-C6 heteroaryl optionally comprises one or more of C1-C6 alkyl, C1-C6 haloalkyl, —O(C1-C6 alkyl), —O(C1-C6 haloalkyl), halo, —CO2H, —CO2Z, —CO2NH2, —O—(CH2CH2O) n -H or -O-(CH2CH2O) n may be substituted with -CH3 groups; -R 5’ is C1-C4 alkyl, C1-C4 haloalkyl, -(CH2CH2O) n -H, -(CH2CH2O) n -CH3, phenyl, or C5-C6 heteroaryl, each of which is -CO2 - and the phenyl or C5-C6 heteroaryl is optionally substituted with one or more of C1-C6 alkyl, C1-C6 haloalkyl, —O(C1-C6 alkyl), —O(C1-C6 haloalkyl), halo, —CO2H, —CO2Z, —CO2NH2, —O—(CH2CH2O) n -H or -O-(CH2CH2O) n may be further substituted with -CH3 groups; -R 6 is -C(O)-OR 3 , -C(O)-SR 3 , -C(O)-N(R 3 )2, -C(S)-OR 3 , -C(S)-SR 3 or -C(S)-N(R 3 )2 is selected; -R 7 is -C(O)-NR 20 R 21 Selected from; -R 8 is one or more of C1-C6 alkyl, C1-C6 haloalkyl, -O(C1-C6 alkyl), -O(C1-C6 haloalkyl), halo, -CO2H, -CO2Z, -CO2NH2, -O-(CH2CH2O) n -H or -O-(CH2CH2O) n -[NC5H5] optionally substituted with -CH3 groups; -R8’ is -CO2 - and substituted with one or more of C1-C6 alkyl, C1-C6 haloalkyl, -O(C1-C6 alkyl), -O(C1-C6 haloalkyl), halo, -CO2H, -CO2Z, -CO2NH2, -O-(CH2CH2O) n -H or -O-(CH2CH2O) n -[NC5H5] optionally further substituted with -CH3 groups; -R 20 is C1-C6 alkyl, preferably C1-C2 or C4-C6 alkyl; -R 21 is H or C1-C6 alkyl; n is 1, 2, 3, 4, 5 or 6; X is a halo group; Y is a counter anion; Z is a counter cation; and M 2+ is a metal cation.

[0168] In one embodiment of this particular preferred embodiment of the first or second aspect of the invention, the compound of formula (I) or the complex of formula (II) is [Table 4] TIFF2025539865000041.tif61159 or any of their enantiomers; or a racemic mixture of either; Or a salt of any of them, not.

[0169] In another embodiment of this particularly preferred embodiment of the first or second aspect of the invention, -R 1 , -R 2 , -R 3 , -R 4 , -R 5 , -R 5’ , -R 6 , -R 8 , -R 8’ , -R α -, -R β, n, X, Y, Z and M 2+ is as defined in any of the embodiments described above for the first aspect of the invention.

[0170] In one embodiment of this particularly preferred embodiment of the first or second aspect of the invention, -R 20 is methyl, ethyl, propyl, butyl, pentyl or hexyl. 20 is methyl, ethyl, butyl, pentyl or hexyl. 20 is butyl.

[0171] In one embodiment of this particularly preferred embodiment of the first or second aspect of the invention, -R 21 is hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl. 21 is hydrogen or methyl.

[0172] Preferably, -R 20 is butyl, and -R 21 is methyl.

[0173] In another particularly preferred embodiment, the first or second aspect of the invention provides a pharmaceutically acceptable salt of a compound of formula (I) or a complex of formula (II): [ka] During the ceremony, -R 1 is -CO2H; -R 6 is -CO2H; -R 7 is -C(O)-OR 22 or -C(O)-NR 20 R 21 and; -R 20 is C1-C6 alkyl; -R 21 is H or C1-C6 alkyl; -R 22is C1-C6 alkyl; M 2+ is a metal cation; Pharmaceutically acceptable salts are lithium, sodium, potassium, magnesium, calcium, ammonium, amine (such as choline or meglumine) or amino acid (such as arginine) salts, or combinations thereof.

[0174] In another embodiment of this particularly preferred embodiment of the first or second aspect of the invention, M 2+ is as defined in any of the embodiments described above for the first aspect of the invention.

[0175] In one embodiment of this particularly preferred embodiment of the first or second aspect of the invention, -R 7 is -C(O)-OR 22 In one embodiment, -R 22 is methyl, ethyl, propyl, butyl, pentyl, or hexyl. 22 is methyl, ethyl, propyl, or butyl. Preferably, -R 22 is methyl or ethyl.

[0176] In another embodiment of this particularly preferred embodiment of the first or second aspect of the invention, -R 7 is -C(O)-NR 20 R 21 In one embodiment, -R 20 is methyl, ethyl, propyl, butyl, pentyl, or hexyl. 21 is hydrogen, methyl, ethyl, propyl, butyl, pentyl, or hexyl. 20 is butyl, and -R 21 is hydrogen or methyl. Preferably, -R 20 is butyl, and -R 21 is methyl.

[0177] In one embodiment, the pharmaceutically acceptable salt is a lithium, sodium, potassium, magnesium, calcium, ammonium, choline, meglumine, arginine salt, or a combination thereof. Preferably, the pharmaceutically acceptable salt is a lithium, sodium, potassium, or meglumine salt, or a combination thereof. Preferably, the pharmaceutically acceptable salt is a sodium or meglumine salt, or a combination thereof.

[0178] In one embodiment, the pharmaceutically acceptable salt is a monosodium salt. In another embodiment, the pharmaceutically acceptable salt is a disodium salt. In another embodiment, the pharmaceutically acceptable salt is a monomeglumine salt. In another embodiment, the pharmaceutically acceptable salt is a dimeglumine salt. In another embodiment, the pharmaceutically acceptable salt is a mixed salt of monosodium and monomeglumine.

[0179] Preferably, in the compound or complex according to the first or second aspect of the invention, the compound or complex comprises: [ka] JPEG2025539865000044.jpg226159JPEG2025539865000045.jpg224159JPEG2025539865000046.jpg231159 JPEG2025539865000047.jpg214159JPEG2025539865000048.jpg173159JPEG2025539865000049.jpg211159JPEG2025539865000050.jpg188159JPEG2025539865000051.jpg198159JPEG2025539865000052.jpg210159JPEG2025539865000053.jpg197159, or a metal cation complex thereof, or a pharmaceutically acceptable salt thereof.

[0180] In one embodiment, the compound or complex according to the first or second aspect of the present invention is in the form of a pharmaceutically acceptable salt. In one embodiment, the compound or complex is in the form of an inorganic salt, such as a lithium, sodium, potassium, magnesium, calcium, or ammonium salt. In one embodiment, the compound or complex is in the form of a sodium or potassium salt. In one embodiment, the compound is in the form of a sodium salt. In another embodiment, the compound or complex is in the form of an organic salt, such as an amine salt (e.g., a choline or meglumine salt) or an amino acid salt (e.g., an arginine salt).

[0181] The compound or complex according to the first or second aspect of the invention has at least two chiral centres. The compound or complex of the first or second aspect of the invention is preferably substantially enantiomerically pure, meaning that the compound or complex contains less than 10% of other stereoisomers, preferably less than 5%, preferably less than 3%, preferably less than 2%, preferably less than 1%, preferably less than 0.5%, all by weight as measured by XRPD or SFC.

[0182] Preferably, the compound or complex according to the first or second aspect of the invention has an HPLC purity of greater than 97%, more preferably greater than 98%, more preferably greater than 99%, more preferably greater than 99.5%, more preferably greater than 99.8%, and most preferably greater than 99.9%. As used herein, % HPLC purity is measured by the area normalization method.

[0183] A third aspect of the invention provides a composition comprising a compound or complex according to the first or second aspect of the invention and a pharmaceutically acceptable carrier or diluent.

[0184] In one embodiment, the composition according to the third aspect of the present invention further comprises polyvinylpyrrolidone (PVP). In one embodiment, the composition comprises 0.01 to 10 wt% PVP as a percentage of the total weight of the composition, preferably 0.1 to 5 wt% PVP as a percentage of the total weight of the composition, preferably 0.5 to 5 wt% PVP as a percentage of the total weight of the composition. In one embodiment, the PVP is K30.

[0185] In one embodiment, the composition according to the third aspect of the present invention further comprises dimethyl sulfoxide (DMSO), hi one embodiment, the composition comprises 0.01 to 99 wt% DMSO as a percentage of the total weight of the composition, preferably 40 to 99 wt% DMSO as a percentage of the total weight of the composition, preferably 65 to 99 wt% DMSO as a percentage of the total weight of the composition.

[0186] In one embodiment, the composition according to the third aspect of the invention further comprises an immune checkpoint inhibitor. In one embodiment, the immune checkpoint inhibitor is an inhibitor of PD-1 (programmed cell death protein 1), PD-L1 (programmed death-ligand 1), or CTLA4 (cytotoxic T-lymphocyte-associated protein 4). In one embodiment, the immune checkpoint inhibitor is selected from pembrolizumab, nivolumab, cemiplimab, atezolizumab, avelumab, durvalumab, or ipilimumab.

[0187] Preferably, the compounds or complexes according to the first or second aspect of the invention, and the pharmaceutical compositions according to the third aspect of the invention, are suitable for use in photodynamic therapy or cytoluminescent therapy.

[0188] Preferably, the compounds or complexes according to the first or second aspect of the invention, and the pharmaceutical compositions according to the third aspect of the invention, are useful for treating atherosclerosis; multiple sclerosis; diabetes; diabetic retinopathy; arthritis; rheumatoid arthritis; fungal, viral, chlamydial, bacterial, nanobacterial or parasitic infections; HIV; AIDS; infection by SARS virus (preferably Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2)), Asian (avian) influenza virus, dengue virus, herpes simplex or shingles; hepatitis; viral hepatitis; cardiovascular disease; coronary artery stenosis; carotid artery stenosis; interstitial pneumonia; Suitable for the treatment of: intermittent claudication; dermatological conditions; acne; psoriasis; diseases characterized by areas of benign or malignant cell hyperproliferation or angiogenesis; benign or malignant tumors; early stage cancer; cervical dysplasia; soft tissue sarcoma; germ cell tumors; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin, or pancreas.

[0189] Preferably, the compounds or complexes according to the first or second aspect of the invention, and the pharmaceutical compositions according to the third aspect of the invention, are suitable for the treatment of diseases characterised by areas of benign or malignant cell hyperproliferation or angiogenesis.

[0190] Preferably, the compounds or complexes according to the first or second aspect of the invention and the pharmaceutical compositions according to the third aspect of the invention are suitable for the treatment of benign or malignant tumours.

[0191] Preferably, the compounds or complexes according to the first or second aspect of the invention, and the pharmaceutical compositions according to the third aspect of the invention, are suitable for the treatment of early stage cancer; cervical dysplasia; soft tissue sarcoma; germ cell tumours; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin or pancreas.

[0192] Preferably, the compounds or complexes according to the first or second aspect of the invention, and the pharmaceutical compositions according to the third aspect of the invention, are suitable for use in photodynamic diagnosis.

[0193] Preferably, the compounds or complexes according to the first or second aspect of the invention, and the pharmaceutical compositions according to the third aspect of the invention, are useful for treating atherosclerosis; multiple sclerosis; diabetes; diabetic retinopathy; arthritis; rheumatoid arthritis; fungal, viral, chlamydial, bacterial, nanobacterial or parasitic infections; HIV; AIDS; infection by SARS virus (preferably Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2)), Asian (avian) influenza virus, dengue virus, herpes simplex or shingles; hepatitis; viral hepatitis; cardiovascular disease; coronary artery stenosis; carotid artery stenosis; interstitial pneumonia; Suitable for detecting intermittent claudication; dermatological conditions; acne; psoriasis; diseases characterized by areas of benign or malignant cellular hyperproliferation or angiogenesis; benign or malignant tumors; early stage cancer; cervical dysplasia; soft tissue sarcoma; germ cell tumors; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin, or pancreas.

[0194] Preferably, the compounds or complexes according to the first or second aspect of the invention and the pharmaceutical compositions according to the third aspect of the invention are suitable for detecting areas affected by benign or malignant cell hyperproliferation or neovascularization.

[0195] Preferably, the compounds or complexes according to the first or second aspect of the invention and the pharmaceutical compositions according to the third aspect of the invention are suitable for the detection of benign or malignant tumours.

[0196] Preferably, the compounds or complexes according to the first or second aspect of the invention, and the pharmaceutical compositions according to the third aspect of the invention, are suitable for the detection of early stage cancer; cervical dysplasia; soft tissue sarcoma; germ cell tumours; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin or pancreas.

[0197] Preferably, the compounds or complexes according to the first or second aspect of the invention, and the pharmaceutical compositions according to the third aspect of the invention, are suitable for the fluorescent or phosphorescent detection of the diseases listed above, preferably for the fluorescent or phosphorescent detection and quantification of the aforementioned diseases.

[0198] Preferably, the compounds or complexes according to the first or second aspect of the invention, and the pharmaceutical compositions according to the third aspect of the invention, are suitable for administration simultaneously with or before the administration of radiation or sound, preferably before the administration of radiation.

[0199] Where the compounds or complexes according to the first or second aspect of the invention, or the pharmaceutical compositions according to the third aspect of the invention, are for use in photodynamic therapy or cytoluminescence therapy, then they are preferably suitable for administration 5 to 100 hours before irradiation, preferably 6 to 72 hours before irradiation, preferably 24 to 48 hours before irradiation.

[0200] When the compounds or complexes according to the first or second aspect of the invention, or the pharmaceutical compositions according to the third aspect of the invention, are for use in photodynamic diagnosis, then they are preferably suitable for administration 3 to 60 hours before irradiation, preferably 8 to 40 hours before irradiation.

[0201] Preferably, the radiation used in photodynamic therapy, cytoluminescence therapy, or photodynamic diagnosis is electromagnetic radiation having a wavelength in the range of 500 nm to 1000 nm, preferably 550 nm to 750 nm, preferably 600 nm to 700 nm, and preferably 640 nm to 670 nm. The electromagnetic radiation can be administered at about 0.1 to 5 W, preferably about 1 W, for about 5 to 60 minutes, preferably about 15 to 20 minutes. In one embodiment of the present invention, two electromagnetic radiation sources (e.g., a laser light and an LED light) are used, both of which are suitable for providing radiation in the wavelength range of 550 nm to 750 nm, preferably 600 nm to 700 nm, and preferably 640 nm to 670 nm. In another embodiment of the present invention, the radiation can be provided by prostate, anal, vaginal, oral, or nasal devices for insertion into body cavities. In another embodiment of the present invention, the radiation can be provided by mediated photoactivation, for example, by inserting a fiber-optic laser into the lung, liver, lymph nodes, or breast using a fine needle. In another embodiment of the invention, illumination may be provided by photoactivation of an endoscope, for example to deliver light to the lungs, stomach, colon, bladder or cervix.

[0202] The pharmaceutical composition according to the third aspect of the present invention may be in a form suitable for oral, parenteral (including intravenous, subcutaneous, intramuscular, intradermal, intratracheal, intraperitoneal, intratumoral, intraarticular, intraperitoneal, intracranial and epidural), transdermal, respiratory (aerosol), rectal, vaginal or topical (including buccal, mucosal and sublingual) administration. The pharmaceutical composition may also be in a form suitable for administration by enema or by injection into a tumor. Preferably, the pharmaceutical composition is in a form suitable for oral, parenteral (such as intravenous, intraperitoneal and intratumoral) or respiratory tract administration, preferably in a form suitable for oral or parenteral administration, preferably in a form suitable for oral administration.

[0203] In one preferred embodiment, the pharmaceutical composition is in a form suitable for oral administration. Preferably, the pharmaceutical composition is provided in the form of tablets, capsules, hard or soft gelatin capsules, caplets, lozenges, or drops; as a powder or granules; or as an aqueous solution, suspension, or dispersion. More preferably, the pharmaceutical composition is provided in the form of an aqueous solution, suspension, or dispersion for oral administration, or in the form of a lyophilized powder that can be mixed with water before administration. Preferably, the pharmaceutical composition is in a form suitable for providing 0.01 to 10 mg / kg / day, preferably 0.1 to 2 mg / kg / day, preferably about 1 mg / kg / day, of a compound or complex according to the first or second aspect of the present invention.

[0204] In another preferred embodiment, the pharmaceutical composition is in a form suitable for parenteral administration. Preferably, the pharmaceutical composition is in a form suitable for intravenous administration. Preferably, the pharmaceutical composition is provided in the form of an aqueous solution for parenteral administration, or in the form of a lyophilized powder that can be mixed with water before administration. Preferably, the pharmaceutical composition is an aqueous solution or suspension having a pH of 6 to 8.5. Preferably, the pharmaceutical composition is in a form suitable for providing 0.01 to 10 mg / kg / day, preferably 0.1 to 2 mg / kg / day, preferably about 1 mg / kg / day, of a compound or complex according to the first or second aspect of the present invention.

[0205] In another preferred embodiment, the pharmaceutical composition is in a form suitable for administration to the respiratory tract. Preferably, the pharmaceutical composition is provided in the form of an aqueous solution, suspension, or dispersion for administration to the respiratory tract, or in the form of a lyophilized powder that can be mixed with water prior to administration to provide an aqueous solution, suspension, or dispersion for administration to the respiratory tract. Preferably, the pharmaceutical composition is in a form suitable for providing 0.01 to 10 mg / kg / day, preferably 0.1 to 2 mg / kg / day, preferably about 1 mg / kg / day, of a compound or complex according to the first or second aspect of the present invention.

[0206] A fourth aspect of the present invention relates to a method for treating atherosclerosis; multiple sclerosis; diabetes; diabetic retinopathy; arthritis; rheumatoid arthritis; fungal, viral, chlamydial, bacterial, nanobacterial or parasitic infections; HIV; AIDS; infection by SARS virus (preferably Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2)), Asian (avian) influenza virus, dengue virus, herpes simplex or shingles; hepatitis; viral hepatitis; cardiovascular disease; coronary artery stenosis; carotid artery stenosis; intermittent claudication; dermatological conditions; acne; psoriasis; benign or malignant cellular hyperproliferation or vascular There is provided use of a compound or complex according to the first or second aspect of the invention in the manufacture of a medicament for the treatment of a disease characterised by areas of neoplasia; a benign or malignant tumour; an early stage cancer; cervical dysplasia; soft tissue sarcoma; a germ cell tumour; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin or pancreas.

[0207] A fourth aspect of the present invention provides the use of a compound or complex according to the first or second aspect of the present invention in the manufacture of a phototherapeutic agent for use in photodynamic therapy or cytoluminescence therapy. Preferably, the phototherapeutic agent is a compound or complex according to the first or second aspect of the present invention for ... atherosclerosis; multiple sclerosis; diabetes; diabetic retinopathy; arthritis; rheumatoid arthritis; fungal, viral, chlamydial, bacterial, nanobacterial or parasitic infection; HIV; AIDS; SARS virus (preferably Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2)), Asian (avian) influenza virus, dengue virus, herpes simplex or shingles infection; hepatitis; viral hepatitis; cardiovascular disease; coronary artery stenosis; carotid artery stenosis; intermittent claudication; dermatological conditions; acne; psoriasis; It is suitable for the treatment of diseases characterized by areas of hyperproliferation of benign or malignant cells or angiogenesis; benign or malignant tumors; early stage cancers; cervical dysplasia; soft tissue sarcoma; germ cell tumors; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin or pancreas.

[0208] Preferably, the medicament or phototherapeutic agent of the fourth aspect of the invention is suitable for the treatment of diseases characterised by areas of benign or malignant cellular hyperproliferation or neovascularisation.

[0209] Preferably, the drug or phototherapeutic agent according to the fourth aspect of the invention is suitable for the treatment of benign or malignant tumours.

[0210] Preferably, the medicament or phototherapeutic agent according to the fourth aspect of the invention is suitable for the treatment of early stage cancer; cervical dysplasia; soft tissue sarcoma; germ cell tumour; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin or pancreas.

[0211] A fourth aspect of the invention also provides the use of a compound or complex according to the first or second aspect of the invention in the manufacture of a photodiagnostic agent for use in photodynamic diagnosis.

[0212] Preferably, the photodiagnostic agent according to the fourth aspect of the present invention is suitable for use in treating atherosclerosis; multiple sclerosis; diabetes; diabetic retinopathy; arthritis; rheumatoid arthritis; fungal, viral, chlamydial, bacterial, nanobacterial or parasitic infections; HIV; AIDS; infection by SARS virus (preferably Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2)), Asian (avian) influenza virus, dengue virus, herpes simplex or shingles; hepatitis; viral hepatitis; cardiovascular disease; coronary artery stenosis; carotid artery stenosis; intermittent claudication; dermatological conditions; acne. ; psoriasis; diseases characterized by areas of benign or malignant cellular hyperproliferation or angiogenesis; benign or malignant tumors; early stage cancer; cervical dysplasia; soft tissue sarcoma; germ cell tumors; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin or pancreas.

[0213] Preferably, the photodiagnostic agent according to the fourth aspect of the present invention is suitable for detecting areas affected by benign or malignant cell hyperproliferation or neovascularization.

[0214] Preferably, the photodiagnostic agent according to the fourth aspect of the present invention is suitable for detecting benign or malignant tumors.

[0215] Preferably, the photodiagnostic agent according to the fourth aspect of the present invention is suitable for the detection of early stage cancer; cervical dysplasia; soft tissue sarcoma; germ cell tumour; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin or pancreas.

[0216] Preferably, the photodiagnostic agent of the fourth aspect of the present invention is suitable for the fluorescent or phosphorescent detection of the aforementioned diseases, preferably for the fluorescent or phosphorescent detection and quantification of the aforementioned diseases.

[0217] Preferably, the drug, phototherapeutic agent or photodiagnostic agent is suitable for administration simultaneously with or before the administration of radiation or sound, preferably before the administration of radiation.

[0218] If the drug or phototherapeutic agent is for use in photodynamic therapy or cytoluminescence therapy, then it is preferably suitable for administration 5 to 100 hours before irradiation, preferably 6 to 72 hours before irradiation, preferably 24 to 48 hours before irradiation.

[0219] If the photodiagnostic agent is used for photodynamic diagnosis, then it is preferably suitable for administration 3 to 60 hours before irradiation, preferably 8 to 40 hours before irradiation.

[0220] Preferably, the radiation used in photodynamic therapy, cytoluminescence therapy, or photodynamic diagnosis is electromagnetic radiation having a wavelength in the range of 500 nm to 1000 nm, preferably 550 nm to 750 nm, preferably 600 nm to 700 nm, and preferably 640 nm to 670 nm. The electromagnetic radiation can be administered at about 0.1 to 5 W, preferably about 1 W, for about 5 to 60 minutes, preferably about 15 to 20 minutes. In one embodiment of the present invention, two electromagnetic radiation sources (e.g., a laser light and an LED light) are used, both of which are suitable for providing radiation in the wavelength range of 550 nm to 750 nm, preferably 600 nm to 700 nm, and preferably 640 nm to 670 nm. In another embodiment of the present invention, the radiation can be provided by prostate, anal, vaginal, oral, or nasal devices for insertion into body cavities. In another embodiment of the present invention, the radiation can be provided by mediated photoactivation, for example, by inserting a fiber-optic laser into the lung, liver, lymph nodes, or breast using a fine needle. In another embodiment of the invention, illumination may be provided by photoactivation of an endoscope, for example to deliver light to the lungs, stomach, colon, bladder or cervix.

[0221] A fifth aspect of the present invention provides a method for treating atherosclerosis; multiple sclerosis; diabetes; diabetic retinopathy; arthritis; rheumatoid arthritis; fungal, viral, chlamydial, bacterial, nanobacterial or parasitic infections; HIV; AIDS; infection by SARS virus (preferably Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2)), Asian (avian) influenza virus, dengue virus, herpes simplex or shingles; hepatitis; viral hepatitis; cardiovascular disease; coronary artery stenosis; carotid artery stenosis; intermittent claudication; dermatological conditions; acne; psoriasis; benign or

[0013] The present invention provides a method for treating a disease characterized by areas of hyperproliferation of malignant cells or angiogenesis; a benign or malignant tumor; early stage cancer; cervical dysplasia; soft tissue sarcoma; germ cell tumor; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin or pancreas, which method comprises administering to a human or animal in need thereof a therapeutically effective amount of a compound or complex according to the first or second aspect of the invention.

[0222] The fifth aspect of the present invention also provides a method for photodynamic or cytoluminescent therapy of a human or animal disease, the method comprising administering to a human or animal in need thereof a therapeutically effective amount of a compound or complex according to the first or second aspect of the present invention. Preferably, the human or animal disease is atherosclerosis; multiple sclerosis; diabetes; diabetic retinopathy; arthritis; rheumatoid arthritis; fungal, viral, chlamydial, bacterial, nanobacterial or parasitic infection; HIV; AIDS; SARS virus (preferably Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2)), Asian (avian) influenza virus, dengue virus, herpes simplex or shingles; hepatitis; viral hepatitis; cardiovascular disease; coronary artery stenosis; carotid artery stenosis; intermittent claudication; dermatological conditions; or acne. ; psoriasis; a disease characterized by areas of benign or malignant cell hyperproliferation or angiogenesis; benign or malignant tumor; early stage cancer; cervical dysplasia; soft tissue sarcoma; germ cell tumor; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin, or pancreas.

[0223] Preferably, the method of the fifth aspect of the invention is a method of treating areas of benign or malignant cellular hyperproliferation or neovascularization.

[0224] Preferably, the method of the fifth aspect of the invention is a method of treating a benign or malignant tumor.

[0225] Preferably, the method of the fifth aspect of the invention is a method of treating early stage cancer; cervical dysplasia; soft tissue sarcoma; germ cell tumors; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin or pancreas.

[0226] The fifth aspect of the invention also provides a method for photodynamic diagnosis of a human or animal disease, the method comprising administering to the human or animal a diagnostically effective amount of a compound or complex according to the first or second aspect of the invention. Preferably, the human or animal disease is atherosclerosis; multiple sclerosis; diabetes; diabetic retinopathy; arthritis; rheumatoid arthritis; fungal, viral, chlamydial, bacterial, nanobacterial or parasitic infection; HIV; AIDS; SARS virus (preferably Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2)), Asian (avian) influenza virus, dengue virus, herpes simplex or shingles; hepatitis; viral hepatitis; cardiovascular disease; coronary artery stenosis; carotid artery stenosis; intermittent claudication; dermatological conditions; acne. psoriasis; diseases characterized by areas of benign or malignant cell hyperproliferation or angiogenesis; benign or malignant tumors; early-stage cancer; cervical dysplasia; soft tissue sarcoma; germ cell tumors; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin, or pancreas. Preferably, the human or animal disease is characterized by benign or malignant cell hyperproliferation or by areas of angiogenesis. Preferably, the human or animal disease is a benign or malignant tumor. Preferably, the human or animal disease is early stage cancer, cervical dysplasia, soft tissue sarcoma, germ cell tumor, retinoblastoma, age-related macular degeneration, lymphoma, Hodgkin's lymphoma, head and neck cancer, oral cancer, or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organ, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin or pancreas. Preferably, the method of photodynamic diagnosis is suitable for fluorescent or phosphorescent detection of the aforementioned diseases, preferably for fluorescent or phosphorescent detection and quantification of the aforementioned diseases.

[0227] In any of the methods of the fifth aspect of the invention, the human or animal is preferably further subjected to irradiation or sound simultaneously with or after administration of a compound or complex according to the first or second aspect of the invention. Preferably, the human or animal is subjected to irradiation after administration of a compound or complex according to the first or second aspect of the invention.

[0228] If the method is a photodynamic therapy or cytoluminescence therapy method, then the human or animal is preferably irradiated 5 to 100 hours after administration of the compound or complex according to the first or second aspect of the invention, preferably 6 to 72 hours, preferably 24 to 48 hours after administration.

[0229] If the method is a method of photodynamic diagnosis, then the human or animal is preferably irradiated 3 to 60 hours, preferably 8 to 40 hours, after administration of the compound or complex according to the first or second aspect of the invention.

[0230] Preferably, the irradiation is electromagnetic radiation having a wavelength in the range of 500 nm to 1000 nm, preferably 550 nm to 750 nm, preferably 600 nm to 700 nm, and preferably 640 nm to 670 nm. The electromagnetic radiation can be administered at about 0.1 to 5 W, preferably about 1 W, for about 5 to 60 minutes, preferably about 15 to 20 minutes. In one embodiment of the present invention, two electromagnetic radiation sources (e.g., a laser light and an LED light) are used, both radiation sources being suitable for providing irradiation at wavelengths in the range of 550 nm to 750 nm, preferably 600 nm to 700 nm, and preferably 640 nm to 670 nm. In another embodiment of the present invention, irradiation can be provided by prostate, anal, vaginal, oral, or nasal devices for insertion into body cavities. In another embodiment of the present invention, irradiation can be provided by mediated photoactivation, for example, by inserting a fiber-optic laser into the lung, liver, lymph nodes, or breast using a fine needle. In another embodiment of the invention, illumination may be provided by photoactivation of an endoscope, for example to deliver light to the lungs, stomach, colon, bladder or cervix.

[0231] In any of the methods of the fifth aspect of the invention, preferably the human or animal is a human.

[0232] A sixth aspect of the present invention is (a) a compound or complex according to the first or second aspect of the present invention, and (b) Providing a drug combination or kit comprising an immune checkpoint inhibitor.

[0233] In one embodiment, the immune checkpoint inhibitor is an inhibitor of PD-1 (programmed cell death protein 1), PD-L1 (programmed death-ligand 1), or CTLA4 (cytotoxic T-lymphocyte-associated protein 4). In one embodiment, the immune checkpoint inhibitor is selected from pembrolizumab, nivolumab, cemiplimab, atezolizumab, avelumab, durvalumab, or ipilimumab.

[0234] Preferably, the combination or kit of the sixth aspect is for use in treating a disease, disorder, or condition, wherein the disease, disorder, or condition is responsive to PD-1, PD-L1, or CTLA4 inhibition. Preferably, the combination or kit of the sixth aspect is for use in treating cancer. In one embodiment, the cancer is melanoma, lung cancer (e.g., non-small cell lung cancer), kidney cancer, bladder cancer, head and neck cancer, or Hodgkin's lymphoma.

[0235] The sixth aspect also provides the use of a combination or kit of the sixth aspect of the invention in the manufacture of a medicament for treating a disease, disorder, or condition responsive to PD-1, PD-L1, or CTLA4 inhibition. The sixth aspect also provides the use of a combination or kit of the sixth aspect of the invention in the manufacture of a medicament for treating cancer. In one embodiment, the cancer is melanoma, lung cancer (e.g., non-small cell lung cancer), kidney cancer, bladder cancer, head and neck cancer, or Hodgkin's lymphoma.

[0236] The sixth aspect of the present invention also provides a method for treating a disease, disorder, or condition responsive to PD-1, PD-L1, or CTLA4 inhibition, comprising administering a therapeutically effective amount of a combination or kit according to the sixth aspect of the present invention to a human or animal in need thereof. The sixth aspect of the present invention also provides a method for treating cancer, comprising administering a therapeutically effective amount of a combination or kit according to the sixth aspect of the present invention to a human or animal in need thereof. In one embodiment, the cancer is melanoma, lung cancer (e.g., non-small cell lung cancer), kidney cancer, bladder cancer, head and neck cancer, or Hodgkin's lymphoma.

[0237] In the case of the combination or kit of the sixth aspect of the invention, the compound or complex according to the first or second aspect of the invention and the immune checkpoint inhibitor may be provided together in one pharmaceutical composition, or may be provided separately in two pharmaceutical compositions, which may be administered at the same time or at different times.

[0238] Preferably, the combination or kit of the sixth aspect is adapted for administration simultaneously with or prior to the administration of irradiation or sound, preferably prior to the administration of irradiation. In one embodiment, the combination or kit of the sixth aspect is suitable for administration 5 to 100 hours prior to irradiation, preferably 6 to 72 hours prior to irradiation, preferably 24 to 48 hours prior to irradiation.

[0239] Preferably, the radiation used in photodynamic therapy or cytoluminescence therapy is electromagnetic radiation having a wavelength in the range of 500 nm to 1000 nm, preferably 550 nm to 750 nm, preferably 600 nm to 700 nm, and preferably 640 nm to 670 nm. The electromagnetic radiation can be administered at about 0.1 to 5 W, preferably about 1 W, for about 5 to 60 minutes, preferably about 15 to 20 minutes. In one embodiment of the present invention, two electromagnetic radiation sources (e.g., a laser light and an LED light) are used, both radiation sources being suitable for providing radiation in the wavelength range of 550 nm to 750 nm, preferably 600 nm to 700 nm, and preferably 640 nm to 670 nm. In another embodiment of the present invention, the radiation can be provided by prostate, anal, vaginal, oral, or nasal devices for insertion into body cavities. In another embodiment of the present invention, the radiation can be provided by mediated photoactivation, for example, by inserting a fiber-optic laser into the lung, liver, lymph nodes, or breast using a fine needle. In another embodiment of the invention, illumination may be provided by photoactivation of an endoscope, for example to deliver light to the lungs, stomach, colon, bladder or cervix.

[0240] For the avoidance of doubt, insofar as is practicable, any embodiment of a given aspect of the invention may be practiced in combination with any other embodiment of the same aspect of the invention. Furthermore, it will be understood that insofar as is practicable, any preferred or optional embodiment of any aspect of the invention shall also be deemed to be a preferred or optional embodiment of any other aspect of the invention.

[0241] Details of the synthesis experiment Chlorin Starting Materials: [ka] JPEG2025539865000055.jpg222159JPEG2025539865000056.jpg124159Synthesis of (2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-((3-aminopropyl)thio)tetrahydro-2H-pyran-3,4,5-triyl triacetate [ka] Step 1: A two-neck 500 mL RBF equipped with a nitrogen inlet and rubber septum was charged with a solution of 1,2,3,4,6-penta-O-acetyl-β-D-glucose (6.23 g, 15.95 mol, 1 equiv.) in dry DCM (150 mL) and a stir bar, and the mixture was placed under N2. To this solution was added (9H-fluoren-9-yl)methyl (3-mercaptopropyl)carbamate (ChemBioChem, 2010, 11(6), 778-781) (6.00 g, 19.1 mmol, 1.2 equiv.), followed by the dropwise addition of BF3·OEt2 (5.9 mL, 47.9 mmol, 3 equiv.) through the rubber septum over 2–3 min. The mixture was stirred (315 rpm) at room temperature under N2 overnight. TLC analysis at this point indicated that only traces of starting material remained. The reaction was quenched by the addition of 1 M HCl (50 mL) and transferred to a separatory funnel. The organic phase was collected and washed with brine (50 mL), then dried (MgSO4) and concentrated by rotary evaporation to give the crude glycosylated product as a pale syrup (18 g). The residue was purified by column chromatography (50% EtOAc / hexane, loaded as a solution in eluent, R f =0.5) to give N-Fmoc-(2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-((3-aminopropyl)thio)tetrahydro-2H-pyran-3,4,5-triyl triacetate as a colorless syrup (5.55 g, 54%) that solidified on standing.

[0242] 1H NMR (400 MHz, CDCl3) δ 7.76 (d, J = 7.4 Hz, 2H), 7.60 (d, J = 7.4 Hz, 2H), 7.39 (dd, J = 7.4, 7.4 Hz, 2H), 7.31 (dd, J = 7.4, 7.4 Hz, 2H), 5.22 (dd, J = 9.4, 9.4 Hz, 1H), 5.05 (dd, J = 9.4, 9.4 Hz, 1H), 5.02 (dd, J = 9.4, 9.4 Hz, 1H), 4.93 (br. s, 1H), 4.50-4.42 (m, 3H), 4.31-4.08 (m, 3H), 3.69 (ddd, J = 10.1, 4.8, 2.7 Hz, 1H), 3.36-3.19 (m, 2H), 2.74 (ddd, J = 13.4, 6.7, 6.7 Hz, 1H), 2.64 (ddd, J = 13.4, 6.7, 6.7 Hz, 1H), 2.05 (s, 3H), 2.04 (s, 3H), 2.03 (s, 3H), 2.00 (s, 3H), 1.87-1.70 (m, 2H).

[0243] Step 2: To a 50 mL flask containing N-Fmoc-(2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-((3-aminopropyl)thio)tetrahydro-2H-pyran-3,4,5-triyl triacetate (633 mg, 0.983 mmol, 2 equiv.) and a stir bar, 20% piperidine / DMF (15 mL) was added, and the resulting solution was stirred (420 rpm) under ambient atmosphere for 10 minutes. An aliquot was taken and 1 Concentration for H NMR analysis indicated cleavage of the Fmoc group. The reaction mixture was concentrated and then reconstituted / concentrated five times from toluene (to remove all piperidine) to give (2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-((3-aminopropyl)thio)tetrahydro-2H-pyran-3,4,5-triyl triacetate as a gummy beige solid, which was used without further purification.

[0244] Synthesis of (2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-((3-thiopropyl)thio)tetrahydro-2H-pyran-3,4,5-triyl triacetate [ka] To a dry, three-necked, 250 mL RBF equipped with a stir bar and stopper was added 1,3-propanedithiol (11.9 g, 110 mmol, 2 equiv.). The flask was fitted with a reflux condenser equipped with a gas inlet and bubbler and then placed under N2. Chloroform (30 mL) was added, and the solution was stirred at room temperature under N2. Using a funnel, 1,2,3,4,6-penta-O-acetyl-β-D-glucose (21.5 g, 55.0 mmol, 1 equiv.) was added and washed with additional chloroform (10 mL). Finally, indium bromide (0.58 g, 1.64 mmol, 0.03 equiv.) was added, and the mixture was placed in a preheated oil bath (90 °C) and stirred under N2 for 2.5 h. The reaction mixture was cooled to room temperature and loaded directly onto a silica gel column (250 × 50 mm) made up of 100% DCM. The column was eluted with 100% DCM, then 30% EtOAc in hexanes, 60% EtOAc in hexanes, and finally 100% EtOAc, collecting 30 × 125 mL fractions. The most intense fractions (11–19), as determined by TLC, were combined and evaporated to give a colorless, viscous oil (10.33 g) that crystallized on standing. 1 H NMR indicated this was the desired product but contained EtOAc (4%) and acetic acid (5%). Therefore, the material was dissolved in DCM (150 mL), washed with 1 M sodium bicarbonate solution (200 mL), and the washes were back-extracted with DCM (50 mL). The combined organic phases were washed with water (150 mL), dried (Na2SO4), and evaporated to give a viscous, colorless oil that rapidly crystallized on standing. The material was triturated with 1:1 hexane / diethyl ether (approximately 30 mL), and larger crystals were crushed with a glass rod. After stirring for 1 h, the suspension was filtered, and the solid was dried overnight in a vacuum oven at 25 °C (7.50 g).

[0245] 1 H NMR (400 MHz, CDCl3) δ 5.21 (dd, J = 9.8, 9.8 Hz, 1H), 5.08 (dd, J = 9.8, 9.8 Hz, 1H), 5.03 (dd, J = 9.8, 9.8 Hz, 1H), 4.49 (d, J = 9.8 Hz, 1H), 4.23 (dd, J = 12.3, 4.9 Hz, 1H), 4.14 (dd, J = 12.3, 2.4 Hz, 1H), 3.71 (ddd, J = 9.8, 4.9, 2.4 Hz, 1H), 2.85 (ddd, J = 12.7, 7.0, 7.0 Hz, 1H), 2.76 (ddd, J = 12.7, 7.0, 7.0 Hz, 1H), 2.63 (app. ddd, J = 8.1, 7.0, 7.0 Hz, 2H), 2.08 (s, 3H), 2.06 (s, 3H), 2.02 (s, 3H), 2.00 (s, 3H), 1.90 (app. p, J = 7.0 Hz, 2H), 1.37 (t, J = 8.1 Hz, 1H).

[0246] Synthesis of (2R,3S,4S,5R,6S)-2-(hydroxymethyl)-6-((3-mercaptopropyl)thio)tetrahydro-2H-pyran-3,4,5-triol [ka] (2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-((3-thiopropyl)thio)tetrahydro-2H-pyran-3,4,5-triyl triacetate (2.50 g, 5.7 mmol, 1 equiv.) was weighed into a 100 mL dry, single-neck RBF, and the flask was equipped with a stir bar and a three-way tap. The flask was placed under N2, and dry MeOH (20 mL) was added via syringe through the three-way tap, while the flask was maintained under N2. Methanolic ammonia (4.8 mL, approximately 57 mmol, 10 equiv.) was added using a graduated pipette, after which the flask was sealed and stirred at room temperature overnight. After 21 hours, the solvent was removed to give (2R,3S,4S,5R,6S)-2-(hydroxymethyl)-6-((3-mercaptopropyl)thio)tetrahydro-2H-pyran-3,4,5-triol (1.74 g) as a clear, pale maroon oil, which was used without further purification.

[0247] 1 H NMR (400 MHz, d4-MeOH) δ 1.92 (quintet, double-acetamide), 2.04 (quintet, 2H (major isomer)), 2.63 (t, 0.6H (minor isomer)), 2.73-2.94 (m, 4.4H), 3.19 (m, 1.3H), 3.25-3.38 (m, duplicate-NMR solvent), 3.62-3.69 (m, 1.3H), 3.83-3.89 (m, 1.3H), 4.34-4.39 (m, 1.3H).

[0248] Synthesis Example 1 - Synthesis of Chlorin e6 Bisβ-D-1-thioglucose propylamide Conjugates 1 and 2 (Compounds 1 and 2) Synthesis of glucose starting material [ka] To a 25 mL flask containing N-Fmoc-3'-amino-1-thio-2,3,4,6-tetra-O-acetyl-β-D-glucopyranose (699 mg, 1.34 mmol, 4 equiv.) and a stir bar, DCM (6.0 mL) and TFA (1.5 mL) were added, and the resulting solution was stirred (300 rpm) under N for 75 min. Aliquots were taken and 1 Concentration for H NMR analysis indicated cleavage of the Boc group. The reaction mixture was concentrated and then reconstituted / concentrated twice from chloroform (15 mL) to give the crude amine as a colorless oil, which was used without further purification.

[0249] Coupling and deprotection [ka] Step 1: A 25 mL RBF containing a stir bar was charged with chlorin e6 (200 mg, 0.3352 mmol, 1 equiv.), PyBOP (610 mg, 1.1732 mmol, 3.5 equiv.), DCM (3.2 mL), and triethylamine (418 μL, 3.0167 mmol, 9 equiv.). The resulting mixture was stirred (420 rpm) for 20 min, and then the (2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-((3-aminopropyl)thio)tetrahydro-2H-pyran-3,4,5-triyl triacetate prepared above was dissolved in DCM (3.2 mL) and added to the mixture. The reaction progress was monitored by HPLC and found to contain a mixture of product and activated intermediate ester, remaining unchanged over 1-2 h. More triethylamine (418 μL, 3.0167 mmol, 9 equiv.) was added, and the reaction was stirred at ambient temperature overnight, at which point the reaction was complete as monitored by HPLC. The reaction mixture was diluted with DCM (8 mL), transferred to a separatory funnel, and washed with 1 M HCl (2 × 15 mL), followed by pH 7 buffer (15 mL). The organic phase was dried (NaSO) and concentrated by rotary evaporation to give 1.0998 g of crude amide as a black film. The residue was found to contain two major products, which were purified by column chromatography (3 × 30 cm) using 5% MeOH / DCM, then 8% MeOH / DCM, and then 10% MeOH / DCM to elute the two compounds. The first peracetic acid chlorin e6 bis complex was obtained as a dark green solid (207.5 mg), and the second peracetic acid chlorin e6 tris complex was obtained as a blue-black solid (265.1 mg). Deacetylation was carried out without further purification.

[0250] Step 2: Chlorin e6 bis-β-D-1-thioglucose propylamide conjugate 1 (compound 1) To a solution of the first peracetic acid chlorin e6 bisβ-1-thioglucose amide complex (207.5 mg, 0.146 mmol, 1 equiv.) in MeOH (7.5 mL) and DCM (5 mL), NaOMe (4.6 M in MeOH, 150 μL, 0.690 mmol, 5 equiv.) was added, and the mixture was stirred (420 rpm) under N for 90 min. TLC analysis showed conversion to the deacetylated product (10% MeOH / DCM, R f (starting material) = 0.31, R f (Product) = 0). The reaction was quenched with AcOH (8 drops) and concentrated by rotary evaporation to give a black film. The residue was purified by column chromatography (3 × 34 cm, packed in 30% MeOH / DCM, using a gradient of 30–50% MeOH / DCM) to give chlorin e6 bisβ-D-1-thioglucose propylamide conjugate 1 (compound 1) as a dark blue-green solid (73.6 mg, 20% yield over two steps).

[0251] 1H NMR (400 MHz, DMSO-d6) δ 9.80 (s, 1H), 9.67 (s, 1H), 9.39-9.33 (m, 1H), 9.14 (s, 1H), 8.37 (dd, J = 17.8, 11.6 Hz, 1H), 7.81 (t, J = 5.6 Hz, 1H), 6.45 (dd, J = 17.8, 1.6 Hz, 1H), 6.15 (dd, J = 11.7, 1.5 Hz, 1H), 5.90-5.84 (m, 1H), 5.80-5.72 (m, 1H), 5.33-5.23 (m, 2H), 5.14 (d, J = 5.6 Hz, 2H), 5.03 (d, J = 4.7 Hz, 1H), 4.92 (d, J = 4.5 Hz, 1H), 4.61 (t, J = 5.8 Hz, 1H), 4.57-4.51 (m, 1H), 4.23 (d, J = 9.0 Hz, 1H), 4.16 (d, J = 9.6 Hz, 1H), 3.88-3.78 (m, 2H), 3.65-3.57 (m, 2H), 3.56 (s, 3H), 3.47 (s, 3H), 3.20-3.00 (m, 6H), 2.99-2.91 (m, 1H), 2.79 (s, 1H), 2.38 (dd, J = 13.8, 6.9 Hz, 1H), 2.18 (s, 1H), 1.82-1.52 (m, 13H), -2.08 (s, 1H), -2.72 (s, 1H). LCMS:C 52 H 71 N6O 14 S2(M+H + ) occasion: 1067.4464; measured value: 1067.4523.

[0252] Process 3: クロリンe6 トリスβ-D-1-チオグルコースプロピルアミド complex 2 (compound 2) To a solution of the second peracetic acid chlorin e6 trisβ-1-thioglucose amide complex (265.1 mg, 0.187 mmol, 1 equiv.) in MeOH (7.5 mL) and DCM (5 mL), NaOMe (4.6 M in MeOH, 150 μL, 0.690 mmol, 5 equiv.) was added, and the mixture was stirred (420 rpm) under N for 90 min. TLC analysis showed conversion to the deacetylated product (10% MeOH / DCM, R f (starting material) = 0.69, R f (Product) = 0). The reaction was quenched with AcOH (8 drops) and concentrated by rotary evaporation to give a black film. The residue was purified by column chromatography (3 × 34 cm, packed in 30% MeOH / DCM, using a gradient of 30–50% MeOH / DCM) to give chlorin e6 trisβ-D-1-thioglucose propylamide conjugate 2 (compound 2) as a dark blue-green solid (48.2 mg, 11% over 2 steps).

[0253] 1 H NMR (400 MHz, DMSO-d6) δ 9.78 (s, 1H), 9.77 (s, 1H), 9.12 (s, 1H), 9.00 (s, 1H), 8.35 (dd, J = 17.8, 11.7 Hz, 1H), 7.97 (s, 1H), 7.82 (t, J = 5.6 Hz, 1H), 6.47 (dd, J = 17.8, 1.6 Hz, 1H), 6.18 (dd, J = 11.6, 1.5 Hz, 1H), 5.21 (d, J = 5.7 Hz, 1H), 5.17-4.88 (m, 10H), 4.62-4.47 (m, 4H), 4.41-4.29 (m, 1H), 4.21 (dd, J = 20.0, 9.6 Hz, 2H), 3.89-3.78 (m, 1H), 3.76-3.58 (m, 2H), 3.55 (s, 3H), 3.51 (s, 3H), 3.12-3.02 (m, 2H), 3.02-2.82 (m, 1H), 2.71-2.55 (m, 3H), 2.22-1.97 (m, 3H), 1.79-1.56 (m, 7H), -1.88 (s, 1H), -2.23 (s, 1H). LCMS:C 61 H 88 N7O 18 S3(M+H + ) : 1302.5342; Actual value: 1302.5357.

[0254] Synthesis Example 2 - Synthesis of chlorin e6 (2-methoxyethyl) methylamine (compound 3) [ka] Step 1: A single-neck 250 mL RBF was charged with chlorin e6 (0.5 g, 1 equiv.), di-tert-butyl dicarbonate ((Boc)O) (188 mg, 1.03 equiv.), and DCM (60 mL). DMAP (8 mg, 0.08 equiv.) was added, and the resulting solution was stirred at 40 °C under a nitrogen atmosphere for 2 h. The resulting black solution was filtered using a cotton plug, and the filtrate was concentrated under reduced pressure. The resulting solid was washed with hexane (2 × 10 mL) and dried to give chlorin e6 anhydride as a black solid (475 mg, 98%), which was used in the next step without further purification.

[0255] 1 H NMR (400 MHz, CDCl3) δ 9.52 (m, 2H), 9.22 (m, 1H), 8.45 (m, 1H), 7.82 (m, 1H), 6.34 (m, 1H), 6.14 (m, 1H), 5.40 (m, 2H), 4.60-4.30 (m, 2H), 3.55 (m, 5H), 3.32 (s, 3H), 3.16 (m, 4H), 2.75-2.50 (m, 2H), 2.35 (m, 2H), 1.95 (m, 1H), 1.75-1.60 (m, 6H), 1.15 (t, 2H), -0.5 (brs, 2H).

[0256] Step 2: A single-neck 250 mL RBF was charged with chlorin e6 anhydride (470 mg, 1 equiv.), (2-methoxyethyl)methylamine (108 mg, 1.5 equiv.), and DCM (30 mL). The resulting solution was stirred overnight at 35 °C under a nitrogen atmosphere. The resulting black solution was concentrated under reduced pressure and precipitated with diethyl ether. The precipitate was filtered and washed with diethyl ether (2 × 10 mL). The remaining black solid was purified by column chromatography using 10–50% MeOH / DCM. Fractions containing the first dark band eluting were combined to give compound 3 as a blue-green solid (320 mg, 59% yield, 95.33% purity by HPLC).

[0257] 1 H NMR (400 MHz, DMSO-d6) δ 9.80 (s, 1H), 9.42 (s, 1H), 9.10 (s, 1H), 8.35 (dd, 1H), 6.44 (d, 1H), 6.14 (d, 1H), 5.20 (m, 1H), 4.50 (m, 1H), 4.30-4.10 (m, 2H), 3.85 (m, 3H), 3.65-3.30 (m, 10H), 3.20 (m, 2H), 2.85 (m, 1H), 2.15 (m, 1H), 1.15 (t, 2H), -2.0 (brs, 1H), -2.68 (brs, 1H).

[0258] Synthesis Example 3 - Synthesis of chlorin e6 (2-methoxyethyl) methylamine dimethyl ester (compound 4) [ka] A single-neck 250 mL RBF was charged with compound 3 (310 g, 1 equiv.), potassium carbonate (192 mg, 3 equiv.), DMF (10 mL), and a stir bar. The flask was placed under nitrogen and stirred at 300 rpm with an air-cooled condenser attached. Methyl iodide (0.072 mL, 3 equiv.) was then added. The solution was stirred at 25 °C over the weekend. The solvent was removed under reduced pressure at 60 °C to give a dark green solid. The crude material was dissolved in DCM (30 mL), washed with water (2 × 10 mL), dried (NaSO), and concentrated under reduced pressure to give the crude product as a dark blue / green solid (350 mg). At this point, HPLC analysis indicated approximately 96% purity. The remaining blue / green solid was purified by column chromatography using 1-5% MeOH / DCM, and the fractions containing the first dark band to elute were combined to give compound 4 as a blue-green solid (310 mg, 98% yield, 98.69% purity by HPLC).

[0259] 1 H NMR (400 MHz, CDCl3) δ 9.70 (s, 1H), 9.55 (m, 1H), 8.72 (m, 1H), 8.10-8.00 (m, 2H), 6.44 (d, 1H), 6.14 (d, 1H), 5.50-5.20 (m, 2H), 4.50 (m, 2H), 4.30-4.10 (m, 2H), 3.90-3.65 (m, 5H), 3.65 (s, 3H), 3.60 (m, 6H), 3.45 (m, 6H), 3.30 (s, 3H), 2.95 (s, 3H), 2.85 (s, 3H), 2.60 (m, 1H), 2.20 (m, 2H), 1.75-1.55 (m, 7H), -1.30 (brs, 1H), -1.45 (brs, 1H).

[0260] Synthesis Example 4 - Synthesis of Chlorin e6 N-methylbutylamine (Compound 5) [ka] A single-neck 250 mL RBF was charged with chlorin e6 anhydride (500 mg, 1 equiv.), N-methylbutylamine (108 mg, 1.5 equiv.), and DCM (30 mL). The resulting solution was stirred overnight at 35 °C under a nitrogen atmosphere. The resulting black solution was concentrated under reduced pressure and precipitated with diethyl ether. The precipitate was filtered, washed with diethyl ether (2 × 10 mL), and dried on a rotavapor to give compound 5 as a blue-green solid (670 mg, quantitative yield, 85.80% purity by HPLC). The crude product was used in the next step without further purification.

[0261] 1 H NMR (400 MHz, DMSO-d6) δ 9.75 (s, 1H), 9.70 (s, 1H), 9.10 (s, 1H), 8.35 (dd, 1H), 6.44 (d, 1H), 6.14 (d, 1H), 5.70 (m, 1H), 5.30 (m, 1H), 4.60 (m, 1H), 4.40 (m, 1H), 3.85 (m, 3H), 3.65-3.40 (m, 10H), 2.85 (m, 1H), 2.40-2.10 (m, 5H), 1.70 (t, 3H), 1.80-1.50 (m, 10H), 1.25 (m, 4H), 1.00 (t, 2H), 0.90 (t, 4H), 0.80 (t, 1H), -1.90 (brs, 1H), -2.35 (brs, 1H).

[0262] Synthesis Example 5 - Synthesis of Chlorin e6 N-methylbutylamine dimethyl ester (Compound 6) [ka] A single-neck 250 mL RBF was charged with compound 5 (650 g, 1 equiv.), potassium carbonate (404 mg, 3 equiv.), DMF (10 mL), and a stir bar. The flask was placed under nitrogen. Methyl iodide (0.150 mL, 2.5 equiv.) was then added. The solution was stirred at 25 °C overnight. The solvent was removed under reduced pressure at 60 °C to give a dark green solid. The crude material was dissolved in DCM (30 mL), washed with water (2 × 10 mL), dried (NaSO), and concentrated under reduced pressure to give compound 6 as a dark blue / green solid (700 mg, quantitative yield, 86.64% purity by HPLC). The crude product was used in the next step without further purification.

[0263] 1 H NMR (400 MHz, CDCl3) δ 9.70 (s, 1H), 9.55 (m, 1H), 8.72 (m, 1H), 8.10-8.00 (m, 2H), 6.44 (d, 1H), 6.14 (d, 1H), 5.50-5.20 (m, 2H), 4.50 (m, 2H), 4.20 (m, 3H), 3.90-3.60 (m, 6H), 3.65 (s, 3H), 3.55 (m, 4H), 3.45 (m, 6H), 3.30 (s, 3H), 2.95 (s, 3H), 2.85 (s, 3H), 2.60 (m, 1H), 2.20 (m, 2H), 1.75-1.55 (m, 9H), 1.40 (m, 1H), 1.10 (t, 1H), 0.90 (t, 3H), -1.30 (brs, 1H), -1.45 (brs, 1H).

[0264] Synthesis Example 6 - Chlorin e6 Synthesis of N-(methylaminopropyl)triphenylphosphonium bromide (compound 7) [ka] A single-neck 100 mL RBF was charged with chlorin e6 anhydride (500 mg, 1 equiv.), (3-(methylamino)propyl)triphenylphosphonium bromide hydrobromide (641 mg, 1.5 equiv.), and DCM (30 mL). The resulting solution was stirred overnight at 35° C. under a nitrogen atmosphere. The resulting black solution was concentrated under reduced pressure and precipitated with diethyl ether. The precipitate was filtered, washed with diethyl ether (2×10 mL), and dried on a rotavapor to give compound 7 as a blue / green solid (1.20 mg, quantitative yield, 72.47% purity by HPLC). The crude product was used in the next step without further purification.

[0265] 1 H NMR (400 MHz, DMSO-d6) δ 9.75 (m, 1H), 9.10 (m, 1H), 9.10 (s, 1H), 8.35 (m, 1H), 8.00-7.75 (m, 11H), 7.65 (m, 3H), 6.44 (d, 1H), 6.14 (d, 1H), 4.60 (m, 1H), 3.85 (m, 3H), 3.65-3.40 (m, 10H), 2.90 (m, 1H), 2.20-2.15 (m, 2H), 1.80-1.50 (m, 6H), 1.00 (t, 2H), -1.90 (brm, 1H), -2.40 (brm, 1H).

[0266] Synthesis Example 7 - Chlorin e6 Synthesis of N-(methylaminopropyl)triphenylphosphonium bromide dimethyl ester (compound 8) [ka] A single-neck 250 mL RBF was charged with compound 7 (1.0 gm, 1 equiv.), potassium carbonate (415 mg, 3 equiv.), DMF (10 mL), and a stir bar. The flask was placed under nitrogen and stirred at 300 rpm with an air-cooled condenser attached. Methyl iodide (0.150 mL, 2.5 equiv.) was then added. The solution was stirred overnight at 30° C. The solvent was removed under reduced pressure at 60° C. to give a dark green solid. The crude material was dissolved in DCM (30 mL), washed with water (2×10 mL), dried (NaSO), and concentrated under reduced pressure to give the crude product as a dark blue / green solid (700 mg). At this point, HPLC analysis indicated approximately 75% purity. The remaining blue / green solid was purified by column chromatography using 2-3% MeOH / DCM, and the fractions containing the first dark band to elute were combined to give compound 8 as a blue / green solid (440 mg, quantitative yield, 99.69% purity by HPLC).

[0267] 1 H NMR (400 MHz, CDCl3) δ 9.60 (s, 1H), 9.50 (s, 1H), 8.70 (s, 1H), 8.10-8.00 (dd, 1H), 7.65 (m, 6H), 7.55 (m, 3H), 7.40 (m, 6H), 6.44 (d, 1H), 6.14 (d, 1H), 5.20 (m, 2H), 4.30 (m, 2H), 4.00-3.90 (m, 5H), 3.70 (m, 3H), 3.65 (s, 3H), 3.55 (s, 3H), 3.40 (s, 3H), 3.30 (s, 3H), 3.20 (s, 3H), 2.60 (m, 1H), 2.20 (m, 4H), 1.70-1.55 (m, 6H), 1.40 (m, 1H), 1.20 (m, 1H), -1.40 (brs, 1H), -1.52 (brs, 1H).

[0268] Synthesis Example 8 - Synthesis of chlorin e6 tetraacetic acid diacid β-D-1-thioglucose-N-methylpropylamide complex (compound 9) [ka] Step 1: To a solution of (2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-((3-((tert-butoxycarbonyl)(methyl)amino)propyl)thio)tetrahydro-2H-pyran-3,4,5-triyl triacetate (0.612 g, 1.14 mmol, 1.4 equiv) in DCM (5 mL) was added TFA (1 mL). The resulting solution was stirred at ambient temperature (420 rpm) for 1 hour and then concentrated by rotary evaporation. The residue was resuspended and concentrated twice from chloroform (2 × 10 mL) to give (2R,3R,4S,5R,6R)-2-(acetoxymethyl)-6-(((3-methylamino)propyl)thio)tetrahydro-2H-pyran-3,4,5-triyl triacetate TFA salt as a viscous oil.

[0269] Step 2: A single-neck 250 mL RBF was charged with chlorin e6 anhydride (2.0 g, 1 equiv.), (2R,3R,4S,5R,6R)-2-(acetoxymethyl)-6-(((3-methylamino)propyl)thio)tetrahydro-2H-pyran-3,4,5-triyl triacetate TFA salt (2.84 g, 1.5 equiv.), sodium bicarbonate (435 mg, 1.5 equiv.), and DCM (30 mL). The resulting solution was stirred overnight at 30° C. under a nitrogen atmosphere. The resulting black solution was concentrated under reduced pressure and precipitated with diethyl ether. The precipitate was filtered, washed with diethyl ether (2×10 mL), and dried on a rotavapor. The remaining black solid was purified by column chromatography using 2-10% MeOH / DCM, and the fractions containing the first dark band to elute were combined and concentrated to give compound 9 as a blue-green solid (1.2 mg, 34% yield, 96.19% purity by HPLC).

[0270] 1H NMR (400 MHz, DMSO-d6) δ 9.75 (s, 1H), 9.70 (s, 1H), 9.10 (s, 1H), 8.35 (dd, 1H), 6.44 (d, 1H), 6.14 (d, 1H), 5.70 (m, 1H), 5.30 (m, 1H), 5.00-4.70 (m, 2H), 4.60 (m, 1H), 4.40 (m, 1H), 4.10-3.85 (m, 5H), 3.55 (m, 10H), 2.75 (m, 2H), 2.40-2.10 (m, 5H), 2.00-1.50 (m, 12H), 1.70 (t, 3H), 1.55 (m, 2H), -1.80 (m, 1H), -2.25 (brs, 1H).

[0271] Synthesis Example 9 - Synthesis of chlorin e6 tetraacetic acid β-D-1-thioglucose-N-methylpropylamide complex dimethyl ester (compound 10) [ka] A single-neck 250 mL RBF was charged with compound 9 (1.0 gm, 1 equiv.), potassium carbonate (490 mg, 3 equiv.), DMF (10 mL), and a stir bar. The flask was placed under nitrogen and stirred at 300 rpm with an air-cooled condenser attached. Methyl iodide (0.218 mL, 2.5 equiv.) was then added. The solution was stirred overnight at 30° C. The solvent was removed under reduced pressure at 60° C. to give a dark green solid. The crude material was dissolved in DCM (30 mL), washed with water (2×10 mL), dried (NaSO), and concentrated under reduced pressure to give the crude product as a dark blue / green solid (approximately 1.2 g). At this point, HPLC analysis indicated approximately 65% ​​purity. The remaining blue / green solid was purified by column chromatography using 2-4% MeOH / DCM, and the fractions containing the first dark band to elute were combined and concentrated to give compound 10 as a blue / green solid (700 mg, 69% yield, 85.89% purity by HPLC).

[0272] 1H NMR (400 MHz, CDCl3) δ 9.70 (s, 1H), 9.55 (s, 1H), 8.70 (s, 1H), 8.10-8.00 (dd, 1H), 6.44 (d, 1H), 6.14 (d, 1H), 5.30-5.00 (m, 3H), 4.50-4.00 (m, 8H), 3.80-3.10 (m, 10H), 3.55 (s, 3H), 3.45 (s, 3H), 3.30 (s, 3H), 2.20-2.00 (m, 15H), 1.80 (m, 5H), -1.20-1.52 (m, 2H).

[0273] Synthesis Example 10 - Synthesis of chlorin e6 N-methylbutylamine bis(N-methyl-D-glucamine) salt (compound 11) [ka] Chlorin e6 N-methylbutylamine (500 mg, 0.751 mmol, 1 equiv.) was weighed into a 25 mL RBF, followed by the addition of distilled deionized water (5 mL) using a stir bar. Meglumine (279 mg, 1.43 mmol, 1.9 equiv.) was added, and the mixture was then stirred with heating at 70 °C for 1 hour. The solution was allowed to cool to ambient temperature and then filtered through a porosity 3 filter (7 cm diameter) into a 250 mL conical flask equipped with a side arm. The reaction flask was rinsed with deionized water (approximately 10 mL), which was passed through the filter to complete the transfer. The filtrate was transferred to a 100 mL RBF using additional deionized water and lyophilized overnight to give compound 11 as a pale green fluffy solid (331 mg, 42% yield, 92.75% purity by HPLC).

[0274] 1H NMR (400 MHz, DMSO-d6) δ 9.80 (s, 1H), 9.66 (s, 1H), 9.12 (s, 1H), 8.36 (ddd, J = 18.0, 11.8, 2.4 Hz, 1H), 6.45 (dd, J = 17.8, 1.7 Hz, 1H), 6.23-6.00 (m, 2H), 5.35 (t, J = 23.3 Hz, 1H), 4.64-4.48 (m, 1H), 4.30 (d, J = 10.6 Hz, 1H), 3.93-3.77 (m, 4H), 3.72 (dd, J = 5.1, 1.5 Hz, 2H), 3.63 (dd, J = 10.8, 3.3 Hz, 2H), 3.57-3.38 (m, 12H), 3.35 (s, 3H), 2.93-2.77 (m, 5H), 2.39 (s, 8H), 1.74-1.66 (m, 2H), 1.63 (d, J = 7.0 Hz, 2H), 1.51 (dt, J = 13.9, 7.5 Hz, 1H), 1.34-1.22 (m, 2H), 0.86 (t, J = 7.3 Hz, 2H), -1.98 (d, J = 14.1 Hz, 1H), -2.56 (d, J = 14.2 Hz, 1H).

[0275] Synthesis Example 11 - Synthesis of chlorin e6 5-methyl ester monosodium mono(N-methyl-D-glucamine) salt (compound 12) [ka] Chlorin e6 5-methyl ester (200 mg, 0.327 mmol, 1 equiv.) was weighed into a 100 mL RBF, followed by the addition of distilled deionized water (30 mL) using a stir bar. Meglumine (64 mg, 0.327 mmol, 1 equiv.) and 0.1 M sodium hydroxide solution (3.27 mL, 0.327 mmol, 1 equiv.) were added, and the mixture was stirred at 25 °C for 2 h. The reaction mixture was then lyophilized overnight (16 h) to give compound 12 as a pale green fluffy solid (253 mg, 93% yield, 85.98% purity by HPLC).

[0276] 1 1H NMR (400 MHz, DMSO-d6) δ 9.74 (s, 1H), 9.68 (s, 1H), 9.11 (s, 1H), 8.29 (dd, J = 17.8, 11.7 Hz, 1H), 6.44 (dd, J = 17.8, 1.6 Hz, 1H), 6.16 (dd, J = 11.6, 1.4 Hz, 1H), 5.29 (d, J = 18.2 Hz, 1H), 5.01 (d, J = 18.1 Hz, 1H), 4.56 (q, J = 7.2 Hz, 1H), 4.48 (d, J = 10.9 Hz, 1H), 4.21 (s, 49H), 3.88 - 3.75 (m, 4H), 3.66 (dd, J = 5.1, 1.5 Hz, 2H), 3.58 (dd, J = 10.8, 3.2 Hz, 2H), 3.54 (s, 14H), 3.51 (s, 3H), 3.47 (dd, J = 5.5, 3.2 Hz, 1H), 3.44 (d, J = 1.4 Hz, 1H), 3.44 - 3.36 (m, 2H), 3.30 (s, 3H), 2.86 (dd, J = 12.3, 3.7 Hz, 2H), 2.78 (dd, J = 12.3, 7.7 Hz, 1H), 2.41 (s, 5H), 2.21 (d, J = 17.0 Hz, 2H), 1.83 (s, 4H), 1.68 (t, J = 7.5 Hz, 7H), -1.71 (s, 1H), -1.99 (s, 1H).

[0277] Synthesis of Synthesis Example 12 - Chlorine e6 5 - Methyl Ester Disodium Salt (Compound 13) [Chemical Structure Diagram] Chlorin e6 5-methyl ester (200 mg, 0.327 mmol, 1 equiv.) was weighed into a 100 mL RBF, followed by the addition of distilled deionized water (30 mL) using a stir bar. 0.1 M sodium hydroxide solution (6.54 mL, 0.654 mmol, 2 equiv.) was added, and the mixture was stirred at 25 °C for 2 h. The reaction mixture was then lyophilized overnight (16 h) to give compound 13 as a fluffy purple solid (216 mg, quantitative yield, 87.74% purity by HPLC).

[0278] 1 H NMR (400 MHz, DMSO-d6) δ 9.73 (s, 1H), 9.69 (s, 1H), 9.10 (s, 1H), 8.30 (dd, J = 17.8, 11.7 Hz, 1H), 6.44 (dd, J = 17.8, 1.6 Hz, 1H), 6.16 (dd, J = 11.6, 1.5 Hz, 1H), 5.38 (d, J = 17.9 Hz, 1H), 4.98 (d, J = 17.9 Hz, 1H), 4.60-4.44 (m, 2H), 4.20 (s, 3H), 3.85-3.77 (m, 4H), 3.54 (s, 3H), 3.51 (s, 3H), 3.31 (s, 3H), 2.29-2.09 (m, 2H), 1.73 (s, 4H), 1.71-1.64 (m, 6H), -1.75 (s, 1H), -2.04 (s, 1H).

[0279] Synthesis Example 13 - Synthesis of chlorin e6 5-methyl ester mono(N-methyl-D-glucamine) salt (compound 14) [ka] Chlorin e6 5-methyl ester (200 mg, 0.327 mmol, 1 equiv.) was weighed into a 100 mL RBF, followed by the addition of distilled deionized water (50 mL) using a stir bar. Meglumine (64 mg, 0.327 mmol, 1 equiv.) was added, and the mixture was stirred at 70 °C for 2 h. The reaction mixture was then lyophilized overnight (16 h) to give compound 14 as a fluffy purple solid (262 mg, 99% yield, 78.36% purity by HPLC).

[0280] 1 H NMR (400 MHz, DMSO-d6) δ 9.73 (s, 1H), 9.64 (s, 1H), 9.08 (s, 1H), 8.26 (dd, J = 17.8, 11.6 Hz, 1H), 6.42 (dd, J = 17.8, 1.6 Hz, 1H), 6.23-6.11 (m, 1H), 5.25-5.06 (m, 4H), 4.58 (q, J = 7.1 Hz, 1H), 4.48-4.41 (m, 1H), 4.21 (s, 3H), 3.89-3.82 (m, 2H), 3.82-3.73 (m, 2H), 3.66 (dd, J = 5.1, 1.6 Hz, 2H), 3.58 (dd, J = 10.8, 3.2 Hz, 2H), 3.53 (s, 3H), 3.50-3.46 (m, 4H), 3.45-3.36 (m, 3H), 3.26 (s, 3H), 2.94 (dd, J = 12.5, 3.5 Hz, 1H), 2.84 (dd, J = 12.4, 8.4 Hz, 1H), 2.65-2.52 (m, 1H), 2.46 (s, 4H), 2.34-2.06 (m, 2H), 1.89 (s, 3H), 1.66 (t, J = 7.3 Hz, 7H), -1.62 (s, 1H), -1.86 (s, 1H).

[0281] Synthesis Example 14-Synthesis of chlorin e6 15-ethyl ester (compound 15) [ka] To a single-neck 500 mL RBF was added chlorin e6 anhydride (3.00 g, 0.005 mol, 1 equiv.), ethanol (4.77 g, 0.103 mol, 2 equiv.), NaHCO3 (13.06 g, 0.155 mol, 10 equiv.), and DCM (150 mL). The resulting solution was stirred (400 rpm) overnight at 35°C under a nitrogen atmosphere. The reaction mixture was then filtered through a sintered glass funnel and concentrated by rotary evaporation to give the crude product as a dark purple-brown solid (approximately 3.0 g). The crude product was purified by column chromatography (silica gel, 4 x 20 cm). The crude product was loaded onto the column as a solution in 10% MeOH / DCM. The product band was eluted from the column using an eluent gradient of 5%, 10%, 15%, and 50% MeOH in DCM. R in 10% MeOH / DCM f Fractions containing a blue-green spot by TLC analysis at HCl = 0.5 were combined and concentrated by rotary evaporation to give compound 15 as a dark blue solid (510 mg, 16% yield, 97.95% purity by HPLC).

[0282] 11H NMR (400 MHz, DMSO-d6) δ 9.75 (s, 1H), 9.69 (s, 1H), 9.11 (s, 1H), 8.32 (dd, J = 17.8, 11.6 Hz, 1H), 6.43 (dd, J = 17.8, 1.6 Hz, 1H), 6.14 (dd, J = 11.6, 1.5 Hz, 1H), 5.80 (d, J = 19.6 Hz, 1H), 5.45 (d, J = 18.8 Hz, 1H), 4.60 (q, J = 7.1 Hz, 1H), 4.37 (d, J = 9.9 Hz, 1H), 4.11 (q, J = 7.1 Hz, 2H), 3.79 (q, J = 7.6 Hz, 2H), 3.51 (d, J = 6.6 Hz, 5H), 3.31 (s, 3H), 2.61 (q, J = 7.8, 7.4 Hz, 0H), 2.32 - 2.19 (m, 1H), 2.12 (q, J = 14.5, 10.1 Hz, 1H), 1.73 - 1.49 (m, 5H), 1.19 (t, J = 7.0 Hz, 3H), -1.89 (s, 1H), -2.36 (s, 1H).

[0283] Synthesis of Example 15 - Chlorin e6 15 - Ethyl Ester Bis(N - Methyl - D - Glucamine) Salt (Compound 16) [Chemical Structure] Chlorin e6 15-ethyl ester (compound 15) (200 mg, 0.320 mmol, 1 equiv.) was weighed into a 25 mL RBF, followed by the addition of distilled deionized water (5 mL) using a stir bar. Meglumine (119 mg, 0.608 mmol, 1.9 equiv.) was added, and the mixture was then stirred with heating at 40 °C for 1 hour. The solution was allowed to cool to ambient temperature, diluted with water (20 mL), and then filtered through a porosity 3 filter (3 cm diameter) into a 250 mL RBF equipped with a side-arm adapter. The reaction flask was rinsed with deionized water (approximately 10 mL), which was passed through the filter to complete the transfer. The filtrate was then lyophilized overnight to afford compound 16 as a dark brown solid (321 mg, 99% yield, 96.95% purity by HPLC).

[0284] 1 H NMR (400 MHz, DMSO-d6) δ 9.80 (s, 1H), 9.68 (s, 1H), 9.13 (s, 1H), 8.36 (dd, J = 17.8, 11.6 Hz, 1H), 6.45 (d, J = 17.9 Hz, 1H), 6.15 (d, J = 11.6 Hz, 1H), 5.98 (d, J = 18.8 Hz, 1H), 5.54 (d, J = 19.0 Hz, 1H), 4.57 (q, J = 7.4 Hz, 1H), 4.37 (d, J = 10.2 Hz, 1H), 4.17-4.03 (m, 2H), 3.90-3.78 (m, 4H), 3.72 (d, J = 5.0 Hz, 2H), 3.62 (dd, J = 10.8, 3.1 Hz, 3H), 3.56-3.41 (m, 19H), 3.34 (s, 3H), 2.89-2.74 (m, 5H), 2.42 (s, 8H), 2.12 (t, J = 12.0 Hz, 2H), 1.70 (t, J = 7.5 Hz, 3H), 1.62 (d, J = 7.0 Hz, 3H), 1.16 (q, J = 9.5, 8.3 Hz, 3H), -2.00 (s, 1H), -2.56 (s, 1H).

[0285] Synthesis Example 16-Synthesis of chlorin e6 15-ethyl ester disodium salt (compound 17) [ka] Chlorin e6 15-ethyl ester (compound 15) (100 mg, 0.160 mmol, 1 equiv.) was weighed into a 100 mL RBF, followed by the addition of distilled deionized water (5 mL) using a stir bar. 0.1 M sodium hydroxide solution (3.04 mL, 0.304 mmol, 1.9 equiv.) was added, and the mixture was stirred at 25 °C for 2 h. The reaction mixture was then lyophilized overnight (16 h) to afford compound 17 as a fluffy purple solid (110 mg, quantitative yield, 72.67% purity by HPLC).

[0286] 1 H NMR (400 MHz, DMSO-d6) δ 9.79 (s, 1H), 9.63 (s, 1H), 9.11 (s, 1H), 8.36 (dd, J = 17.8, 11.6 Hz, 1H), 6.44 (dd, J = 17.8, 1.7 Hz, 1H), 6.23-6.05 (m, 2H), 5.39 (d, J = 18.6 Hz, 1H), 4.56 (q, J = 7.2 Hz, 1H), 4.27 (d, J = 10.1 Hz, 1H), 4.10 (q, J = 6.9 Hz, 2H), 3.83 (q, J = 7.5 Hz, 2H), 3.55 (s, 3H), 3.45 (s, 2H), 3.34 (s, 2H), 2.33-2.24 (m, 1H), 2.09 (q, J = 7.1 Hz, 1H), 2.05-1.93 (m, 1H), 1.70 (t, J = 7.5 Hz, 3H), 1.65 (s, 1H), 1.54-1.42 (m, 1H), 1.17 (t, J = 7.1 Hz, 5H), -2.00 (s, 1H), -2.63 (s, 1H).

[0287] Synthesis Example 17 - Synthesis of chlorin e6 15-ethyl ester mono(N-methyl-D-glucamine) salt (compound 18) [ka] Chlorin e6 15-ethyl ester (compound 15) (100 mg, 0.160 mmol, 1 equiv.) was weighed into a 25 mL RBF, followed by the addition of distilled deionized water (5 mL) using a stir bar. Meglumine (31 mg, 0.160 mmol, 1 equiv.) was added, and the mixture was stirred at 40 °C for 2 h. The reaction mixture was then lyophilized overnight (16 h) to give compound 18 as a dark brown fluffy solid (132 mg, quantitative yield, 93.03% purity by HPLC).

[0288] 1 H NMR (400 MHz, DMSO-d6) δ 9.79 (s, 1H), 9.67 (s, 1H), 9.12 (s, 1H), 8.36 (dd, J = 17.8, 11.7 Hz, 1H), 6.44 (d, J = 17.8 Hz, 1H), 6.15 (d, J = 11.6 Hz, 1H), 5.97 (d, J = 18.7 Hz, 1H), 5.50 (d, J = 19.0 Hz, 1H), 4.66-4.50 (m, 1H), 4.35 (d, J = 10.1 Hz, 1H), 4.09 (q, J = 7.0 Hz, 2H), 3.91-3.76 (m, 3H), 3.72 (d, J = 4.9 Hz, 1H), 3.61 (dd, J = 10.8, 2.9 Hz, 2H), 3.55-3.52 (m, 4H), 3.47 (s, 3H), 3.34 (s, 3H), 2.91-2.76 (m, 3H), 2.44 (s, 5H), 2.14 (d, J = 10.8 Hz, 2H), 1.69 (t, J = 7.5 Hz, 3H), 1.61 (d, J = 7.0 Hz, 2H), 1.16 (t, J = 7.1 Hz, 3H), -2.01 (s, 1H), -2.58 (s, 1H).

[0289] Synthesis Example 18-Synthesis of chlorin e6 15-(3-((triphenylphosphonium) chloride) propyl) ester (compound 19) [ka] To a single-neck 250 mL RBF was added chlorin e6 anhydride (1.00 g, 1.73 mmol, 1 equiv.), (3-hydroxypropyl)triphenylphosphonium chloride (6.16 g, 17.3 mmol, 10 equiv.), NaHCO3 (2.91 g, 34.6 mmol, 20 equiv.), and DCM (70 mL). The resulting solution was stirred (400 rpm) at 35 °C under a nitrogen atmosphere for 24 h. The progress of the reaction was monitored by HPLC. The reaction mixture was filtered through a sintered glass funnel and concentrated by rotary evaporation to give the crude product as a dark purple-brown solid. The crude product was purified by column chromatography. The crude product was loaded onto the column as a solution in 10% MeOH / DCM. An eluent gradient of 10%, 20%, 35%, and 50% MeOH in DCM was used to elute the product band from the column (final major band). R in 10% MeOH / DCM f Fractions containing a blue-green spot by TLC analysis at =0.6 were combined and concentrated by rotary evaporation to give compound 19 as a dark blue solid.

[0290] 11H NMR (400 MHz, DMSO-d6) δ 9.81 (s, 1H), 9.62 (s, 1H), 9.11 (s, 1H), 8.36 (dd, J = 17.8, 11.6 Hz, 1H), 7.89 - 7.73 (m, 6H), 7.69 - 7.59 (m, 3H), 7.46 (td, J = 7.8, 3.2 Hz, 6H), 6.43 (dd, J = 17.8, 1.6 Hz, 1H), 6.14 (dd, J = 11.6, 1.5 Hz, 1H), 4.60 (q, J = 7.2 Hz, 1H), 4.43 (s, 1H), 4.19 (d, J = 24.5 Hz, 3H), 3.95 (d, J = 13.2 Hz, 0H), 3.83 (d, J = 7.6 Hz, 1H), 3.52 (s, 2H), 3.37 - 3.35 (m, 6H), 2.65 - 2.54 (m, 1H), 2.26 - 2.07 (m, 2H), 1.69 (t, J = 7.5 Hz, 3H), 1.59 (d, J = 7.1 Hz, 3H), -1.98 (s, 1H), -2.56 (s, 1H).

[0291] Synthesis of Example 19 - Chlorin e6 5 - Methyl Ester Bis(N - Methyl - D - Glucamine) Salt (Compound 20) [Chemical Structure] A 50 mL RBF containing chlorin e6 5-methyl ester (300 mg, 0.491 mmol, 1 equiv.) was charged with distilled deionized water (10 mL) and a stir bar (approximately 20 mm). The mixture was heated with stirring (200 rpm) at 70 °C for 30 min in the dark. Meglumine (192 mg, 0.982 mmol, 2 equiv.) was added, and the mixture was then stirred at 70 °C in the dark under nitrogen for 3 h. The solution was stirred (30 min) and allowed to cool to ambient temperature, then filtered through a 3-pore size filter into a 500 mL conical flask equipped with a side arm. The reaction flask was rinsed with distilled deionized water (2 × 5 mL) to remove any remaining residue. The filtrate was transferred to a 250 mL RBF, and the solution was lyophilized overnight to give compound 20 as a powdery brown / black solid (0.44 g, 89%).

[0292] 1 H NMR (400 MHz, d6-DMSO) δ 9.72 (s, 1H), 9.67 (s, 1H), 9.09 (s, 1H), 8.38 (dd, 1H), 6.43 (dd, 1H), 6.16 (dd, 1H), 5.16 (d, 1H), 5.01 (d, 1H), 4.58-4.46 (m), 4.19 (s), 3.83-3.77 (m, 7H), 3.66-3.63 (m), 3.61-3.56 (m), 3.55-3.45 (m), 3.45-3.36 (m), 3.29 (s, 3H), 2.86-2.79 (m, 3H), 2.78-2.72 (m, 3H), 2.39 (s, 8H), 2.20-2.12 (m, 2H), 1.70-1.66 (m, 7H), -1.69 (brs, 1H), -1.97 (brs, 1H).

[0293] Synthesis Example 20-Synthesis of chlorin e6 15-butyl ester (compound 21) [ka] To a single-neck 250 mL RBF was added chlorin e6 anhydride (1.00 g, 1.73 mmol, 1 equiv.), n-butanol (2.56 g, 34.6 mmol, 20 equiv.), NaHCO3 (4.36 g, 51.8 mmol, 30 equiv.), and DCM (50 mL). The resulting solution was stirred overnight at 35 °C under a nitrogen atmosphere. The reaction mixture was then filtered through a sintered glass funnel and concentrated by rotary evaporation to give the crude product as a dark purple-brown solid (1.9 g). The crude product was purified by column chromatography. The crude product was loaded onto the column as a solution in 5% MeOH / DCM. An eluent gradient of 5 to 10% MeOH in DCM was used to elute the product band from the column. R in 10% MeOH / DCM was added. f Fractions containing a blue-green spot by TLC analysis at =0.3 were combined and concentrated by rotary evaporation to give compound 21 as a dark blue-green solid (520 mg).

[0294] 1H NMR (400 MHz, DMSO-d6) δ 9.75 (s, 1H), 9.69 (s, 1H), 9.11 (s, 1H), 8.32 (dd, J = 17.8, 11.6 Hz, 1H), 6.43 (dd, J = 17.8, 1.6 Hz, 1H), 6.14 (dd, J = 11.6, 1.5 Hz, 1H), 5.80 (d, J = 19.6 Hz, 1H), 5.45 (d, J = 18.8 Hz, 1H), 4.60 (q, J = 7.1 Hz, 1H), 4.37 (d, J = 9.9 Hz, 1H), 4.11 (q, J = 7.1 Hz, 2H), 3.79 (q, J = 7.6 Hz, 2H), 3.51 (d, J = 6.6 Hz, 5H), 3.31 (s, 3H), 2.61 (q, J = 7.8, 7.4 Hz, 0H), 2.32-2.19 (m, 1H), 2.12 (q, J = 14.5, 10.1 Hz, 1H), 1.73-1.49 (m, 6H), 1.50 (m, 2H), 1.20 (m, 2H), 1.19 (t, J = 7.0 Hz, 3H), -1.60 (s, 1H), -1.90 (s, 1H).

[0295] Synthesis Example 21-Synthesis of クロリンe6 15-ヘキシルエステル (Compound 22)

change

[0296] 1 H NMR (400 MHz, DMSO-d6) δ 9.74 (s, 1H), 9.63 (s, 1H), 9.08 (s, 1H), 8.23 ​​(dd, 1H), 6.40 (dd, 1H), 6.12 (dd, 1H), 5.51-5.39 (m, 2H), 4.60 (q, 1H), 4.44 (d, 1H), 4.04 (m, 2H), 3.75 (q, 2H), 3.57 (s, 3H), 3.47 (s, 3H), 3.24 (s, 3H), 2.68-2.55 (m, 1H), 2.28-2.18 (m, 1H), 2.17-2.09 (m, 1H), 1.69-1.62 (m, 6H), 1.61-1.55 (m, 1H), 1.52-1.45 (m, 2H), 1.10-0.97 (m, 6H), 0.61 (t, 3H), -1.63 (brs, 1H), -1.89 (brs, 1H).

[0297] Biological experiment details Example 1 - Determination of the Solubility of Chlorin e6 Analogues The absorbance maximum was used as a surrogate measure of solubility. The relevant chlorin e6 analogs were diluted to 50 μM in PBS (phosphate-buffered saline) solutions containing decreasing amounts of DMSO from 100% to 0%.

[0298] Where necessary, polyvinylpyrrolidone (K30) was added to a final concentration of 1% w / v. Absorbance was measured using a Cytation 3 multimode plate reader (Biotek) in spectral scanning mode, with spectra captured from 500 to 800 nm in 2 nm increments. An equivalent volume of blank solution was also measured and subtracted accordingly. Each spectrum was normalized to have a minimum signal of 0 and a maximum signal in 100% pure DMSO solution (the most soluble state).

[0299] Example 2 - Cytotoxicity, Phototoxicity and Therapeutic Index Preparation of photosensitizer stock solutions Photosensitizers (e.g., chlorin e6 analog, chlorin e4 disodium (provided by Advanced Molecular Technologies, Scoresby) or talaporfin sodium (purchased from Focus Bioscience, catalog number HY-16477-5MG)) were resuspended in 100% dimethyl sulfoxide (DMSO) at a concentration of 5.5 mM. Samples were stored at 4°C protected from light.

[0300] Preparation of photosensitizers for in vitro testing For in vitro testing, photosensitizer (stock solution, 5.5 mM in 100% DMSO) was diluted 1:100 in concentrated excipient solution (10% w / v Kollidon-12, 42.4% w / v polysorbate 80, 0.6% w / v anhydrous citric acid, 40% w / v ethanol, 1.0% DMSO, final concentration of 55 μM photosensitizer). Serial dilutions were prepared in cell culture medium (Dulbecco's modified Eagle's medium / nutrient mixture F-12 (DMEM / F-12)) supplemented with 10% v / v fetal bovine serum, 100 U / mL penicillin, 100 μg / mL streptomycin, and the same excipient solution at a constant 1:55 dilution.

[0301] cell culture The human ovarian cancer cell line SKOV3 (ATCC #HTB-77) was maintained in Dulbecco's modified Eagle's medium / nutrient mixture F-12 (DMEM / F-12) supplemented with 10% (v / v) fetal bovine serum, 100 U / mL penicillin, and 100 μg / mL streptomycin. Monolayer cultures were grown in a humidified incubator at 37°C with 5% CO. When cells reached approximately 80% confluence, spent medium was replaced with medium containing the photosensitizer at the required concentration, and the cells were incubated for the desired period to allow for uptake of the photosensitizer.

[0302] statistical analysis All data were analyzed using GraphPad PRISM v8.3.1(549) (GraphPad Software, CA). Spectral absorbance and viability measurements were normalized to a range of 0–100%, and the minimum and maximum values ​​were determined from the data set. Dose-response was determined using sigmoidal four-point nonlinear regression with variable slope, and the IC10 or IC90 was calculated for each compound. All data are presented as mean ± SD (where applicable).

[0303] cytotoxicity SKOV3 cells were seeded into 96-well black-walled plates (Greiner #655090) at a cell density of 5000 cells per well in 100 μl of medium. Upon reaching approximately 60% confluence, the medium was aspirated and replaced with fresh medium containing 0–100 μM of the relevant chlorin e6 analog in DMSO. Cells were incubated for an additional 24 h to allow for uptake of the chlorin e6 analog.

[0304] To test the intrinsic cytotoxicity (i.e., "dark toxicity") of chlorin e6 analogs, the culture medium was replaced with fresh medium containing 10% (v / v) AlamarBlue cell viability reagent (ThermoFisher) after 24 h, and the cells were incubated at 37 °C for 6 h. Untreated cells were used as a control. Fluorescence emission (Ex 555 nm / Em 596 nm) was measured using a Cytation 3 cell imaging multimode reader (Biotek), and cytotoxicity was assessed by the percentage of viable cells remaining. All measurements were performed in quadruplicate.

[0305] phototoxicity SKOV3 cells were seeded into 96-well black-walled plates (Greiner #655090) at a cell density of 5000 cells per well in 100 μl of medium. Upon reaching approximately 60% confluence, the medium was aspirated and replaced with fresh medium containing 0–100 μM of the relevant chlorin e6 analog in DMSO. Cells were incubated for an additional 24 h to allow for uptake of the chlorin e6 analog.

[0306] To test for phototoxicity, cells incubated with chlorin e6 analogs (0–10 μM in DMSO) were exposed to 50 mW / cm light after 24 h with a medium change (as above) and then to 50 mW / cm light. 2 The specimen was exposed to a 652 nm laser (Invion) ​​for 5 min at a laser density of 15 J / cm2 (total). 2 After activation, cells were cultured for an additional 24 hours. The medium was then replaced with fresh medium containing AlamarBlue, and the survival rate of viable cells was assessed as described above. Controls included cells treated with chlorin e6 analogs but not activated by laser light, cells not treated with chlorin e6 analogs but irradiated with laser light, and an untreated control. All measurements were performed in quadruplicate.

[0307] Toxicity profiles of chlorin e6 analogues The phototoxicity and intrinsic cytotoxicity (i.e., "dark toxicity") of chlorin e6 analogs were evaluated using SKOV3 ovarian cancer cells as previously described. For comparison purposes, chlorin e6 analogs were compared with chlorin e4 disodium and talaporfin sodium, a clinically approved photosensitizer used in the photodynamic therapy of lung cancer. Phototoxicity IC90 and dark toxicity IC10 values ​​were calculated using the log[inhibitor]-versus-normalized dose-response curve and variable slope according to the formula Y = 100 / (1 + (IC90 / X)^HillSlope(phototoxicity IC90)) or Y = 100 / (1 + (IC10 / X)^HillSlope(dark toxicity IC10)).

[0308] Chlorin e4 disodium and talaporfin sodium had substantially less phototoxicity in vitro than compounds 1, 2, and 8.

[0309] Therapeutic index of chlorin e6 analogues To assess the therapeutic potential of chlorin e6 analogs, the therapeutic index (TI) was calculated. TI provides a quantitative measure that describes relative drug safety by comparing the drug concentration required for the desired effect with the concentration that results in undesired off-target toxicity. TI was calculated using the phototoxicity IC90 versus the dark toxicity IC10.

[0310] The TI values ​​are shown in Table 1. Talaporfin sodium had the lowest therapeutic index (TI = 0.49), and chlorin e4 disodium was only slightly better (TI = 1.89), indicating that they have lower relative cytotoxicity but a smaller potential therapeutic window of use. The chlorin e6 analogs of the present invention had significantly improved TIs with substantially greater phototoxicity (Table 1).

[0311] Therefore, the chlorin e6 analogs of the present invention have a desirable therapeutic index that is better than that of clinically applied photosensitizers. Furthermore, the greater phototoxicity of chlorin e6 analogs suggests the possibility of their use at significantly reduced doses in vivo. Therefore, the chlorin e6 analogs have an acceptable therapeutic profile for clinical application. [Table 5]

[0312] Example 3 - Stability study of chlorin e6 analogue salts in aqueous solution procedure Reaction solutions were prepared by dissolving 2-3 mg of each chlorin e6 analog salt in 5 mL of distilled, deionized water in a 50 mL test tube with a lid. The solution was stirred in the test tube at 30 °C. Air (oxygen) and ambient light were not excluded. HPLC analysis of the samples was performed at 0.5, 4, or 66 hours (unless otherwise indicated). The purpose was to examine degradation over time. The test results are summarized in Table 2 below. [Table 6] Table 2: HPLC purity of chlorin e6 analogue salts in aqueous solution after 0.5, 4 and 66 hours (unless otherwise indicated). *Material was approximately 77.7% pure by HPLC at the start.

[0313] The structures of photoron and photodithiazine are as follows: [ka]

[0314] HPLC method Column and instrument details Equipment: Waters Alignment HPLC equipped with a Waters e2695 separation module and a Waters 2998 PDA detector. Column: YMC-Pack Pro C18 / S-3μm / 12nm 150 x 4.6mml. DS / N: 112YB00270 Guard column: Phenomenex Security Guard Cartridge C18 4 x 3.0 mm IDPRD-281272

[0315] [Table 7] Mobile phase: A = 0.05 w / v% phosphoric acid in distilled water, B = acetonitrile Injection volume: 5 μL HPLC run length: 35 min Detection wavelength: 406 nm Column temperature: 40℃

[0316] conclusion As can be seen from the experimental results, -R 7 An ester or amide group (e.g., —C(O)—R , as defined in the description and claims) 14 -R 15 , -C(O)-NR 20 R 21 or -C(O)-OR 22 Compounds that have a hydroxyl group are more stable in aqueous solution than compounds that do not have such a group.

[0317] It will be understood that the present invention has been described above by way of example only, and that the examples are not intended to limit the scope of the invention. Various modifications and embodiments can be made without departing from the scope and spirit of the invention, which is defined solely by the claims that follow.

Claims

1. A compound of formula (I) or a complex of formula (II), 【Chemistry 1】 or a pharmaceutically acceptable salt thereof, wherein: -R １ is -CH ２ OR ２ , -CH ２ SR ２ , -CH ２ S(O)R ２ , -CH ２ S (O) ２ R ２ , -CH ２ N (R ２ ) ２ , -R ２ , —C(O)—OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ２ is, independently of each other, H, -C(O)R ４ , -C(O)-OR ４ , -C(O)-SR ４ , -C(O)-N(R ４ ), ２ , -C(S)-OR ４ , -C(S)-SR ４ , -C(S)-N(R ４ ), ２ , -R α -H, -R β , -R α , -R β , -R α , -OH, -R α , -OR β , -R α , -SH, -R α , -SR β , -R α , -S(O)R β , -R α , -S(O) ２ R β , -R α [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ -R ３ and -R ４ are each independently -H, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O) ２ R β , -R α -NH ２ , -R α -NH(R β ), -R α -N(R β ) ２ , -R α -X, -R α -[N(R ５ ) ３ ] Y, -R α -[P(R ５ ) ３ ] Y, -R α - [R ８ ] Y, -R α -[N(R ５ ) ２ (R ５’ ) ], -R α -[P(R ５ ) ２ (R ５’ ) or R α - [R ８’ ] is selected from; -R α - are each independently C １ -C ４２ alkylene groups, which optionally include one or more C １ -C ４ Alkyl, C １ -C ４ It may be substituted with a haloalkyl or halo group, and one or more carbon atoms of the backbone of the alkylene group may optionally be replaced by a heteroatom or group independently selected from O, S, NH, or NMe; -R β are each independently a saturated or unsaturated hydrocarbyl group which may be linear or branched or may be or include a cyclic group which may be optionally substituted and which may optionally include one or more heteroatoms N, O, S, P or Se in its carbon skeleton; -R ５ are each independently C １ -C ４ Alkyl, C １ -C ４ Haloalkyl, -(CH ２ CH ２ O) ｎ -H, -(CH ２ CH ２ O) ｎ -CH ３ , phenyl or C ５ -C ６ heteroaryl, phenyl or C ５ -C ６ Heteroaryl optionally includes one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ may be substituted with a group; -R ５’ is C １ -C ４ Alkyl, C １ -C ４ Haloalkyl, -(CH ２ CH ２ O) ｎ -H, -(CH ２ CH ２ O) ｎ -CH ３ , phenyl or C ５ -C ６ heteroaryl, each of which is —CO ２ － and substituted with phenyl or C ５ -C ６ Heteroaryl optionally includes one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ may be further substituted with groups; -R ６ is -C(O)-OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ７ is -C(O)-OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ８ is one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ -[NC optionally substituted with a group ５ H ５ ] and -R ８’ is -CO ２ － and one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ -[NC] optionally further substituted with a group ５ H ５ ] and n is 1, 2, 3, 4, 5 or 6; X is a halo group; Y is a counter anion; Z is a counter cation; and M ２＋ is a metal cation; However, the compound or the complex is (1) (7S,8S)-7-(2-carboxyethyl)-5-(carboxymethyl)-18-ethyl-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-3-carboxylic acid [chlorin e6]; (2) (7S,8S)-18-ethyl-5-(2-methoxy-2-oxoethyl)-7-(3-methoxy-3-oxopropyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-3-carboxylic acid; (3) 2-((7S,8S)-18-ethyl-7-(3-methoxy-3-oxopropyl)-3-(methoxycarbonyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-5-yl)acetic acid; (4) 3-((7S,8S)-18-ethyl-5-(2-methoxy-2-oxoethyl)-3-(methoxycarbonyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-7-yl)propanoic acid; (5) (7S,8S)-5-(carboxymethyl)-18-ethyl-7-(3-methoxy-3-oxopropyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-3-carboxylic acid; (6) (7S,8S)-7-(2-carboxyethyl)-18-ethyl-5-(2-methoxy-2-oxoethyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-3-carboxylic acid; (7) 3-((7S,8S)-5-(carboxymethyl)-18-ethyl-3-(methoxycarbonyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-7-yl)propanoic acid; (8) Methyl (7S,8S)-18-ethyl-5-(2-methoxy-2-oxoethyl)-7-(3-methoxy-3-oxopropyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-3-carboxylate [chlorin e6 trimethyl ester]; (9) methyl 3-(3-carbamoyl-18-ethyl-5-(2-methoxy-2-oxoethyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-7-yl)propanoate; (10) methyl 3-(18-ethyl-5-(2-methoxy-2-oxoethyl)-2,8,12,17-tetramethyl-3-(methylcarbamoyl)-13-vinyl-7H,8H-porphyrin-7-yl)propanoate; (11) methyl 3-(18-ethyl-3-(ethylcarbamoyl)-5-(2-methoxy-2-oxoethyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-7-yl)propanoate; (12) methyl 3-(3-(benzoylcarbamoyl)-18-ethyl-5-(2-methoxy-2-oxoethyl)-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-7-yl)propanoate; (13) methyl 3-(18-ethyl-5-(2-methoxy-2-oxoethyl)-2,8,12,17-tetramethyl-3-(piperidine-1-carbonyl)-13-vinyl-7H,8H-porphyrin-7-yl)propanoate; (14) 5-(2-((3-((5-amino-1-carboxypentyl)carbamoyl)-17-(carboxymethyl)-14-(3-guanidinopropyl)-20-(hydroxymethyl)-1,9,12,15,18,21-hexaoxodocosahydro-7H-pyrrolo[2,1-g][1,2]dithia[5,8,11,14,17,20]hexaazacyclotricosin-8-yl)amino)-2-oxoethyl)-7-(2-carboxyethyl)-18-ethyl-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-3-carboxylic acid; (15) (4-((2-(2-(3-carboxy-7-(2-carboxyethyl)-18-ethyl-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-5-yl)acetamido)ethyl)amino)-4-oxobutyl)triphenylphosphonium chloride; (16) (1-(3-carboxy-5-(2,13-dioxo-16-(triphenylphosphonio)-6,9-dioxa-3,12-diazahexadecyl)-18-ethyl-2,8,12,17-tetramethyl-13-vinyl-7H,8H-porphyrin-7-yl)-3,14-dioxo-7,10-dioxa-4,13-diazaheptadecan-17-yl)triphenylphosphonium dichloride; or a salt thereof.

2. Each -R α - is independently C １ -C ６ 2. The compound or complex of claim 1, wherein the alkylene is selected from the group consisting of alkylenes.

3. -R ２ , -R ３ and -R ４ At least one of the α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O) ２ R β -R β 5. A compound or complex according to any preceding claim, wherein is a saccharidyl group.

4. -R β teeth, 【Chemistry 2】 4. The compound or complex of claim 3, wherein the saccharidyl group is selected from:

5. The saccharidyl group is 【Transformation 3】 5. The compound or complex of claim 4, wherein:

6. -R β teeth, 【Chemistry 4】 is a saccharidyl group selected from In the formula, -R ９ is C １ -C ４ 4. The compound or complex of claim 3, wherein the alkyl is selected from the group consisting of alkyl, methyl ...

7. -R ９ The compound or complex of claim 6, wherein is methyl.

8. -R １ is -C(O)-OR ３ and R ３ Ha-R β and -R β is C １ -C ４ 10. A compound or complex according to any preceding claim, which is an alkyl group.

9. -R １ is -C(O)-OR ３ , —C(O)—SR ３ or —C(O)—N(R ３ ) (R ３’ ) selected from -R ３ is -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O) ２ R β -R β is a saccharidyl group, and -R ３’ is H or C １ -C ４ The compound or complex according to any one of claims 1 to 7, which is alkyl.

10. -R ６ is -C(O)-OR ３ and -R ３ is C １ -C ４ 10. A compound or complex according to any preceding claim, wherein the compound or complex is alkyl.

11. -R ６ is -C(O)-OR ３ , —C(O)—SR ３ or —C(O)—N(R ３ ) (R ３’ ) selected from -R ３ is -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O) ２ R β -R β is a saccharidyl group, and -R ３’ is H or C １ -C ４ 10. The compound or complex of any one of claims 1 to 9, which is alkyl.

12. -R ７ is -C(O)-OR ３ and -R ３ is C １ -C ４ 10. A compound or complex according to any preceding claim, wherein the compound or complex is alkyl.

13. -R ７ is -C(O)-OR ３ , —C(O)—SR ３ or —C(O)—N(R ３ ) (R ３’ ) selected from -R ３ is -R α -OR β , -R α -SR β , -R α -S(O)R β or -R α -S(O) ２ R β -R β is a saccharidyl group, and -R ３’ is H or C １ -C ４ 12. The compound or complex of any one of claims 1 to 11, which is alkyl.

14. A compound of formula (I) or a complex of formula (II): 【Transformation 5】 or a pharmaceutically acceptable salt thereof, wherein: -R １ is -CO ２ H or -CO ２ R １３ Selected from: -R ６ is -CO ２ H or -CO ２ R １３ Selected from: -R ７ is -C(O)-R １４ -R １５ Selected from: -R １３ is C １ -C ３ alkyl; -R １４ - is selected from NMe, O or S; -R １５ is C １ -C ２０ alkyl, wherein one or more carbon atoms of the alkyl group may be optionally substituted with a heteroatom or group independently selected from O, S, NH, or NMe, and the alkyl group may be selected from one or more -OH or -NH ２ may be optionally substituted with a group; M ２＋ is a metal cation; However, -R ７ is -CO ２ Me group or —CO ２ provided that it is not an Et group, However, the compound of formula (I) or the complex of formula (II) is Table 1 or any enantiomer thereof; or a racemic mixture of either thereof; or any salt thereof, provided that said compound or said complex is not

15. A compound of formula (I) or a complex of formula (II), 【Transformation 6】 or a pharmaceutically acceptable salt thereof, wherein: -R １ is -CO ２ H or -CO ２ R １３ Selected from: -R ６ is -CO ２ H or -CO ２ R １３ Selected from: -R ７ is -C(O)-R １４ -R １５ Selected from: -R １３ is C １ -C ３ alkyl; -R １４ - is selected from NH, NMe, O or S; -R １５ is C ４ -C ２０ alkyl, wherein one or more carbon atoms of the alkyl group may be optionally substituted with a heteroatom or group independently selected from O, S, NH, or NMe, and the alkyl group may be selected from one or more -OH or -NH ２ may be optionally substituted with a group; M ２＋ is a metal cation; However, -R ７ is -CO ２ Me group or —CO ２ provided that it is not an Et group, However, the compound of formula (I) or the complex of formula (II) is Table 2 or any enantiomer thereof; or a racemic mixture of either thereof; or any salt thereof, provided that said compound or said complex is not

16. A compound of formula (I) or a complex of formula (II), 【Transformation 7】 or a pharmaceutically acceptable salt thereof, wherein: -R １ is -CH ２ OR ２ , -CH ２ SR ２ , -CH ２ S(O)R ２ , -CH ２ S (O) ２ R ２ , -CH ２ N (R ２ ) ２ , -R ２ , —C(O)—OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ２ is, independently of each other, H, -C(O)R ４ , -C(O)-OR ４ , -C(O)-SR ４ , -C(O)-N(R ４ ), ２ , -C(S)-OR ４ , -C(S)-SR ４ , -C(S)-N(R ４ ), ２ , -R α -H, -R β , -R α -R β , -R α -OH, -R[[ID=3i]] α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O) ２ R β , -R i α -NH ２ , -R α -NH(R β ), -R α -N(R β ), ２ i , -R α -X, -R α -[N(R ５ ), ３ Y, -R α -[P(R ５ ), ３ Y, -R α -[R ８ Y, -R α -[N(R ５ ), ２ (R ５’ i ), -R α -[P(R ５ ), ２ (R ５’ ), or -R<C α -[R ８’ and is selected from; -R ３ and -R ４ are each independently -H, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O) ２ R β , -R α -NH ２ , -R α -NH(R β ), -R α -N(R β ) ２ , -R α -X, -R α -[N(R ５ ) ３ ] Y, -R α -[P(R ５ ) ３ ] Y, -R α - [R ８ ] Y, -R α -[N(R ５ ) ２ (R ５’ ) ], -R α -[P(R ５ ) ２ (R ５’ ) or R α - [R ８’ ] is selected from; -R α - are each independently C １ -C ４２ alkylene groups, which optionally include one or more C １ -C ４ Alkyl, C １ -C ４ It may be substituted with a haloalkyl or halo group, and one or more carbon atoms of the backbone of the alkylene group may optionally be replaced by a heteroatom or group independently selected from O, S, NH, or NMe; -R β are each independently a saturated or unsaturated hydrocarbyl group which may be linear or branched or may be or include a cyclic group which may be optionally substituted and which may optionally include one or more heteroatoms N, O, S, P or Se in its carbon skeleton; -R ５ are each independently C １ -C ４ Alkyl, C １ -C ４ Haloalkyl, -(CH ２ CH ２ O) ｎ -H, -(CH ２ CH ２ O) ｎ -CH ３ , phenyl or C ５ -C ６ heteroaryl, phenyl or C ５ -C ６ Heteroaryl optionally includes one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ may be substituted with a group; -R ５’ is C １ -C ４ Alkyl, C １ -C ４ Haloalkyl, -(CH ２ CH ２ O) ｎ -H, -(CH ２ CH ２ O) ｎ -CH ３ , phenyl or C ５ -C ６ heteroaryl, each of which is —CO ２ － and substituted with phenyl or C ５ -C ６ Heteroaryl optionally includes one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ may be further substituted with groups; -R ６ is -C(O)-OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ７ is -C(O)-OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ８ is one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ -[NC optionally substituted with a group ５ H ５ ] and -R ８’ is -CO ２ － and one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ -[NC] optionally further substituted with a group ５ H ５ ] and n is 1, 2, 3, 4, 5 or 6; X is a halo group; Y is a counter anion; Z is a counter cation; and M ２＋ is a metal cation; However, -R １ , -R ６ , and -R ７ At least one of the α - [R ８ ]Y or -R α - [R ８’ and wherein the compound or the complex comprises:

17. A compound of formula (I) or a complex of formula (II), 【Transformation 8】 or a pharmaceutically acceptable salt thereof, wherein: -R １ is -CH ２ OR ２ , -CH ２ SR ２ , -CH ２ S(O)R ２ , -CH ２ S (O) ２ R ２ , -CH ２ N (R ２ ) ２ , -R ２ , —C(O)—OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ２ is, independently of each other, H, -C(O)R ４ , -C(O)-OR ４ , -C(O)-SR ４ , -C(O)-N(R ４ ), ２ , -C(S)-OR ４ , -C(S)-SR ４ , -C(S)-N(R ４ ), ２ , -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR<000071​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ -R ３ and -R ４ are each independently -H, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O) ２ R β , -R α -NH ２ , -R α -NH(R β ), -R α -N(R β ) ２ , -R α -X, -R α -[N(R ５ ) ３ ] Y, -R α -[P(R ５ ) ３ ] Y, -R α - [R ８ ] Y, -R α -[N(R ５ ) ２ (R ５’ ) ], -R α -[P(R ５ ) ２ (R ５’ ) or R α - [R ８’ ] is selected from; -R α - are each independently C １ -C ４２ alkylene groups, which optionally include one or more C １ -C ４ Alkyl, C １ -C ４ It may be substituted with a haloalkyl or halo group, and one or more carbon atoms of the backbone of the alkylene group may optionally be replaced by a heteroatom or group independently selected from O, S, NH, or NMe; -R β are each independently a saturated or unsaturated hydrocarbyl group which may be linear or branched or may be or include a cyclic group which may be optionally substituted and which may optionally include one or more heteroatoms N, O, S, P or Se in its carbon skeleton; -R ５ are each independently C １ -C ４ Alkyl, C １ -C ４ Haloalkyl, -(CH ２ CH ２ O) ｎ -H, -(CH ２ CH ２ O) ｎ -CH ３ , phenyl or C ５ -C ６ heteroaryl, phenyl or C ５ -C ６ Heteroaryl optionally includes one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ may be substituted with a group; -R ５’ is C １ -C ４ Alkyl, C １ -C ４ Haloalkyl, -(CH ２ CH ２ O) ｎ -H, -(CH ２ CH ２ O) ｎ -CH ３ , phenyl or C ５ -C ６ heteroaryl, each of which is —CO ２ － and substituted with phenyl or C ５ -C ６ Heteroaryl optionally includes one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ may be further substituted with groups; -R ６ is -C(O)-OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ７ is -C(O)-OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ８ is one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ -[NC optionally substituted with a group ５ H ５ ] and -R ８’ is -CO ２ － and one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ -[NC] optionally further substituted with a group ５ H ５ ] and n is 1, 2, 3, 4, 5 or 6; X is a halo group; Y is a counter anion; Z is a counter cation; and M ２＋ is a metal cation; However, -R １ , -R ６ and -R ７ At least one of the １４ - [(CH ２ ) ｐ O) ] ｒ - (CH ２ ) ｓ -R １４ -R １６ wherein: Each -R １４ - is independently selected from NH, NMe, O, or S; -R １６ is a saccharidyl group; p is 1, 2, 3 or 4; r is 0, 1, 2, 3, 4, 5 or 6; The compound or the complex, wherein s is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

18. A compound of formula (I) or a complex of formula (II), 【Chemistry 9】 or a pharmaceutically acceptable salt thereof, wherein: -R １ is -CH ２ OR ２ , -CH ２ SR ２ , -CH ２ S(O)R ２ , -CH ２ S (O) ２ R ２ , -CH ２ N (R ２ ) ２ , -R ２ , —C(O)—OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ２ is, independently of each other, H, -C(O)R ４ , -C(O)-OR ４ , -C(O)-SR ４ , -C(O)-N(R ４ ) ２ , -C(S)-OR ４ , -C(S)-SR ４ , -C(S)-N(R ４ ) ２ , -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O) ２ R β , -R α -NH ２ , -R α -NH(R β ), -R α -N(R β ) ２ , -R α -X, -R α -[N(R ５ ) ３ Y, -R α -[P(R ５ ) ３ Y, -R α -[R ８ Y, -R α -[N(R ５ ) ２ (R ５’ )], -R α -[P(R ５ ) ２ (R ５’ )] or -R α -[R ８’ and is selected from; -R ３ and -R ４ are each independently -H, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O) ２ R β , -R α -NH ２ , -R α -NH(R β ), -R α -N(R β ) ２ , -R α -X, -R α -[N(R ５ ) ３ ] Y, -R α -[P(R ５ ) ３ ] Y, -R α - [R ８ ] Y, -R α -[N(R ５ ) ２ (R ５’ ) ], -R α -[P(R ５ ) ２ (R ５’ ) or R α - [R ８’ ] is selected from; -R α - are each independently C １ -C ４２ alkylene groups, which optionally include one or more C １ -C ４ Alkyl, C １ -C ４ It may be substituted with a haloalkyl or halo group, and one or more carbon atoms of the backbone of the alkylene group may optionally be replaced by a heteroatom or group independently selected from O, S, NH, or NMe; -R β are each independently a saturated or unsaturated hydrocarbyl group which may be linear or branched or may be or include a cyclic group which may be optionally substituted and which may optionally include one or more heteroatoms N, O, S, P or Se in its carbon skeleton; -R ５ are each independently C １ -C ４ Alkyl, C １ -C ４ Haloalkyl, -(CH ２ CH ２ O) ｎ -H, -(CH ２ CH ２ O) ｎ -CH ３ , phenyl or C ５ -C ６ heteroaryl, phenyl or C ５ -C ６ Heteroaryl optionally includes one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ may be substituted with a group; -R ５’ is C １ -C ４ Alkyl, C １ -C ４ Haloalkyl, -(CH ２ CH ２ O) ｎ -H, -(CH ２ CH ２ O) ｎ -CH ３ , phenyl or C ５ -C ６ heteroaryl, each of which is —CO ２ － and substituted with phenyl or C ５ -C ６ Heteroaryl optionally includes one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ may be further substituted with groups; -R ６ is -C(O)-OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ７ is -C(O)-OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ８ is one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ -[NC optionally substituted with a group ５ H ５ ] and -R ８’ is -CO ２ － and one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ -[NC] optionally further substituted with a group ５ H ５ ] and n is 1, 2, 3, 4, 5 or 6; X is a halo group; Y is a counter anion; Z is a counter cation; and M ２＋ is a metal cation; However, -R １ , -R ６ and -R ７ At least one of the １４ - [(CH ２ ) ｐ -R １４ ] ｒ - (CH ２ ) ｓ -R １７ wherein: Each -R １４ - is independently selected from NH, NMe, O, or S; -R １７ is -[P(R ５ ) ３ ]Y or -[P(R ５ ) ２ (R ５’ ) ]; p is 1, 2, 3 or 4; r is 0, 1, 2, 3, 4, 5 or 6; The compound or the complex, wherein s is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

19. A compound of formula (I) or a complex of formula (II), 【Chemistry 10】 or a pharmaceutically acceptable salt thereof, wherein: -R １ is -CH ２ OR ２ , -CH ２ SR ２ , -CH ２ S(O)R ２ , -CH ２ S (O) ２ R ２ , -CH ２ N (R ２ ) ２ , -R ２ , —C(O)—OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ２ is, independently of each other, H, -C(O)R ４ , -C(O)-OR ４ , -C(O)-SR ４ , -C(O)-N(R ４ ), ２ , -C(S)-OR ４ , -C(S)-SR ４ , -C(S)-N(R ４ ), ２ , -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O) ２ R β , -R α -NH ２ , -R α -NH(R β ), -R α -N(R β ), ２ , -R α -X, -R α -[N(R ５ ), ３ Y, -R α -[P(R ５ ), ３ Y, -R α -[R ８ Y, -R α -[N(R ５ ), ２ ５’ (R α ), -R ５ -[P(R ２ ), ５’ (R α ), ８’ -[Ror -R selected from; -R ３ and -R ４ are each independently -H, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O) ２ R β , -R α -NH ２ , -R α -NH(R β ), -R α -N(R β ) ２ , -R α -X, -R α -[N(R ５ ) ３ ] Y, -R α -[P(R ５ ) ３ ] Y, -R α - [R ８ ] Y, -R α -[N(R ５ ) ２ (R ５’ ) ], -R α -[P(R ５ ) ２ (R ５’ ) or R α - [R ８’ ] is selected from; -R α - are each independently C １ -C ４２ alkylene groups, which optionally include one or more C １ -C ４ Alkyl, C １ -C ４ It may be substituted with a haloalkyl or halo group, and one or more carbon atoms of the backbone of the alkylene group may optionally be replaced by a heteroatom or group independently selected from O, S, NH, or NMe; -R β are each independently a saturated or unsaturated hydrocarbyl group which may be linear or branched or may be or include a cyclic group which may be optionally substituted and which may optionally include one or more heteroatoms N, O, S, P or Se in its carbon skeleton; -R ５ are each independently C １ -C ４ Alkyl, C １ -C ４ Haloalkyl, -(CH ２ CH ２ O) ｎ -H, -(CH ２ CH ２ O) ｎ -CH ３ , phenyl or C ５ -C ６ heteroaryl, phenyl or C ５ -C ６ Heteroaryl optionally includes one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ may be substituted with a group; -R ５’ is C １ -C ４ Alkyl, C １ -C ４ Haloalkyl, -(CH ２ CH ２ O) ｎ -H, -(CH ２ CH ２ O) ｎ -CH ３ , phenyl or C ５ -C ６ heteroaryl, each of which is —CO ２ － and substituted with phenyl or C ５ -C ６ Heteroaryl optionally includes one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ may be further substituted with groups; -R ６ is -C(O)-OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ７ is -C(O)-OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ８ is one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ -[NC optionally substituted with a group ５ H ５ ] and -R ８’ is -CO ２ － and one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ -[NC] optionally further substituted with a group ５ H ５ ] and n is 1, 2, 3, 4, 5 or 6; X is a halo group; Y is a counter anion; Z is a counter cation; and M ２＋ is a metal cation; However, -R １ , -R ６ and -R ７ At least one of (i)-R １４ - [(CH ２ ) ｐ -R １４ ] ｒ - (CH ２ ) ｓ -R １８ [In the formula, Each -R １４ - is independently selected from NH, NMe, O, or S; -R １８ is -[N(R ５ ) ３ ]Y or -[N(R ５ ) ２ (R ５’ ) ]; p is 1, 2, 3 or 4; r is 2, 3, 4, 5 or 6; s is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12; or (ii)-R １４ - (CH ２ ) ｓ -R １８ [In the formula, -R １４ - is selected from NH, NMe, O or S; -R １８ is -[N(R ５ ) ３ ]Y or -[N(R ５ ) ２ (R ５’ ) ]; and s is 4, 5, 6, 7, 8, 9, 10, 11 or 12.

20. A compound of formula (I) or a complex of formula (II), 【Chemistry 11】 or a pharmaceutically acceptable salt thereof, wherein: -R １ is -CH ２ OR ２ , -CH ２ SR ２ , -CH ２ S(O)R ２ , -CH ２ S (O) ２ R ２ , -CH ２ N (R ２ ) ２ , -R ２ , —C(O)—OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ２ is, independently of each other, H, -C(O)R ４ , -C(O)-OR ４ , -C(O)-SR ４ , -C(O)-N(R ４ ), ２ , -C(S)-OR ４ , -C(S)-SR ４ , -C(S)-N(R ４ ), ２ , -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O) ２ R β , -R α -NH ２ , -R α -NH(R β ), -R α -N(R β ), ２ , -R α -X, -R α -[N(R[[ID=6​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ -R ３ and -R ４ are each independently -H, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O) ２ R β , -R α -NH ２ , -R α -NH(R β ), -R α -N(R β ) ２ , -R α -X, -R α -[N(R ５ ) ３ ] Y, -R α -[P(R ５ ) ３ ] Y, -R α - [R ８ ] Y, -R α -[N(R ５ ) ２ (R ５’ ) ], -R α -[P(R ５ ) ２ (R ５’ ) or R α - [R ８’ ] is selected from; -R α - are each independently C １ -C ４２ alkylene groups, which optionally include one or more C １ -C ４ Alkyl, C １ -C ４ It may be substituted with a haloalkyl or halo group, and one or more carbon atoms of the backbone of the alkylene group may optionally be replaced by a heteroatom or group independently selected from O, S, NH, or NMe; -R β are each independently a saturated or unsaturated hydrocarbyl group which may be linear or branched or may be or include a cyclic group which may be optionally substituted and which may optionally include one or more heteroatoms N, O, S, P or Se in its carbon skeleton; -R ５ are each independently C １ -C ４ Alkyl, C １ -C ４ Haloalkyl, -(CH ２ CH ２ O) ｎ -H, -(CH ２ CH ２ O) ｎ -CH ３ , phenyl or C ５ -C ６ heteroaryl, phenyl or C ５ -C ６ Heteroaryl optionally includes one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ may be substituted with a group; -R ５’ is C １ -C ４ Alkyl, C １ -C ４ Haloalkyl, -(CH ２ CH ２ O) ｎ -H, -(CH ２ CH ２ O) ｎ -CH ３ , phenyl or C ５ -C ６ heteroaryl, each of which is —CO ２ － and substituted with phenyl or C ５ -C ６ Heteroaryl optionally includes one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ may be further substituted with groups; -R ６ is -C(O)-OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ７ is -C(O)-OR １９ Selected from: -R ８ is one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ -[NC optionally substituted with a group ５ H ５ ] and -R ８’ is -CO ２ － and one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ -[NC] optionally further substituted with a group ５ H ５ ] and -R １９ is C ３ -C ６ is alkyl; n is 1, 2, 3, 4, 5 or 6; X is a halo group; Y is a counter anion; Z is a counter cation; and M ２＋ is a metal cation; However, the compound of formula (I) or the complex of formula (II) is Table 3 or any enantiomer thereof; or a racemic mixture of either thereof; or any salt thereof, provided that said compound or said complex is not

21. A compound of formula (I) or a complex of formula (II), 【Chemistry 12】 or a pharmaceutically acceptable salt thereof, wherein: -R １ is -CH ２ OR ２ , -CH ２ SR ２ , -CH ２ S(O)R ２ , -CH ２ S (O) ２ R ２ , -CH ２ N (R ２ ) ２ , -R ２ , —C(O)—OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ２ is, independently of each other, H, -C(O)R ４ , -C(O)-OR ４ , -C(O)-SR ４ , -C(O)-N(R ４ ), ２ , -C(S)-OR ４ , -C(S)-SR ４ , -C(S)-N(R<...>), ２ , -R α , -H, -R β , -R α , -R β , -R α , -OH, -R<0...>, -OR β , -R α , -SH, -R α ... , -SR β , -R α , -S(O)R β , -R α , -S(O) ２ R β , -R α , -NH ２ , -R α , -NH(R β ), -R α , -N(R β ), ２ , -R α , -X, -R α , -[N(R ５ ), ３ , -R α , -[P(R ５ ), ３ , -R α , -[R ８ , -R α , -[N(R ５ ), ２ (R ５’ ), -R α , -[P(R ５ ), ２ (R ５’ ), or -R α , -[R ８’ , is selected from; -R ３ and -R ４ are each independently -H, -R α -H, -R β , -R α -R β , -R α -OH, -R α -OR β , -R α -SH, -R α -SR β , -R α -S(O)R β , -R α -S(O) ２ R β , -R α -NH ２ , -R α -NH(R β ), -R α -N(R β ) ２ , -R α -X, -R α -[N(R ５ ) ３ ] Y, -R α -[P(R ５ ) ３ ] Y, -R α - [R ８ ] Y, -R α -[N(R ５ ) ２ (R ５’ ) ], -R α -[P(R ５ ) ２ (R ５’ ) or R α - [R ８’ ] is selected from; -R α - are each independently C １ -C ４２ alkylene groups, which optionally include one or more C １ -C ４ Alkyl, C １ -C ４ It may be substituted with a haloalkyl or halo group, and one or more carbon atoms of the backbone of the alkylene group may optionally be replaced by a heteroatom or group independently selected from O, S, NH, or NMe; -R β are each independently a saturated or unsaturated hydrocarbyl group which may be linear or branched or may be or include a cyclic group which may be optionally substituted and which may optionally include one or more heteroatoms N, O, S, P or Se in its carbon skeleton; -R ５ are each independently C １ -C ４ Alkyl, C １ -C ４ Haloalkyl, -(CH ２ CH ２ O) ｎ -H, -(CH ２ CH ２ O) ｎ -CH ３ , phenyl or C ５ -C ６ heteroaryl, phenyl or C ５ -C ６ Heteroaryl optionally includes one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ may be substituted with a group; -R ５’ is C １ -C ４ Alkyl, C １ -C ４ Haloalkyl, -(CH ２ CH ２ O) ｎ -H, -(CH ２ CH ２ O) ｎ -CH ３ , phenyl or C ５ -C ６ heteroaryl, each of which is —CO ２ － and substituted with phenyl or C ５ -C ６ Heteroaryl optionally includes one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ may be further substituted with groups; -R ６ is -C(O)-OR ３ , —C(O)—SR ３ , -C(O)-N(R ３ ) ２ , -C(S)-OR ３ , -C(S)-SR ３ or -C(S)-N(R ３ ) ２ Selected from: -R ７ is —C(O)—NR ２０ R ２１ Selected from: -R ８ is one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ -[NC optionally substituted with a group ５ H ５ ] and -R ８’ is -CO ２ － and one or more C １ -C ６ Alkyl, C １ -C ６ haloalkyl, —O(C １ -C ６ alkyl), —O(C １ -C ６ haloalkyl), halo, —CO ２ H, -CO ２ Z, -CO ２ NH ２ , —O—(CH ２ CH ２ O) ｎ -H or -O-(CH ２ CH ２ O) ｎ -CH ３ -[NC] optionally further substituted with a group ５ H ５ ] and -R ２０ is C １ -C ６ Alkyl, preferably C １ -C ２ or C ４ -C ６ is alkyl; -R ２１ is H or C １ -C ６ is alkyl; n is 1, 2, 3, 4, 5 or 6; X is a halo group; Y is a counter anion; Z is a counter cation; and M ２＋ is a metal cation; However, the compound of formula (I) or the complex of formula (II) is Table 4 【change】 or any enantiomer thereof; or a racemic mixture of either thereof; or any salt thereof, provided that said compound or said complex is not

22. A pharmaceutically acceptable salt of a compound of formula (I) or a complex of formula (II): 【Chemistry 13】 During the ceremony, -R １ is -CO ２ H; -R ６ is -CO ２ H; -R ７ is -C(O)-OR ２２ or —C(O)—NR ２０ R ２１ and -R ２０ is C １ -C ６ is alkyl; -R ２１ is H or C １ -C ６ is alkyl; -R ２２ is C １ -C ６ is alkyl; M ２＋ is a metal cation; The pharmaceutically acceptable salt is a lithium, sodium, potassium, magnesium, calcium, ammonium, amine (such as choline or meglumine) or amino acid (such as arginine) salt, or a combination thereof.

23. The compound or the complex is 【Chemistry 14】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 or a metal cation complex thereof, or a pharmaceutically acceptable salt thereof.

24. 10. A compound or complex according to any preceding claim for use in medicine.

25. 10. A compound or complex according to any preceding claim for use in photodynamic therapy or cytoluminescent therapy.

26. atherosclerosis; multiple sclerosis; diabetes; diabetic retinopathy; arthritis; rheumatoid arthritis; fungal, viral, chlamydial, bacterial, nanobacterial or parasitic infection; HIV; AIDS; infection by SARS virus (preferably Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2)), Asian (Chicken) Influenza virus, Dengue virus, Herpes simplex or Herpes zoster; hepatitis; viral hepatitis; cardiovascular disease; coronary artery stenosis; carotid artery stenosis; intermittent claudication; dermatological conditions; acne; psoriasis; benign or malignant cell hyperproliferation or 10. A compound or complex as claimed in any preceding claim for use in the treatment of diseases characterised by areas of angiogenesis; benign or malignant tumours; early stage cancers; cervical dysplasia; soft tissue sarcoma; germ cell tumours; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin or pancreas.

27. 10. A compound or complex according to any preceding claim for use in the treatment of a disease characterised by benign or malignant cellular hyperproliferation or by areas of neovascularisation.

28. 10. A compound or complex according to any preceding claim for use in the treatment of benign or malignant tumors.

29. 10. A compound or complex as claimed in any preceding claim for use in the treatment of early stage cancer; cervical dysplasia; soft tissue sarcoma; germ cell tumor; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin or pancreas.

30. 10. A compound or complex according to any preceding claim for use in photodynamic diagnosis.

31. 10. A compound or complex according to any preceding claim, wherein the compound is suitable for administration prior to the administration of radiation.

32. 32. The compound or complex of claim 31, wherein the radiation is electromagnetic radiation having a wavelength in the range of 500 nm to 1000 nm.

33. A pharmaceutical composition comprising a compound or complex according to any preceding claim and a pharmaceutically acceptable carrier or diluent.

34. 34. The pharmaceutical composition of claim 33, further comprising polyvinylpyrrolidone.

35. 35. The pharmaceutical composition of claim 33 or 34, further comprising an immune checkpoint inhibitor.

36. 36. The pharmaceutical composition of claim 35, wherein the immune checkpoint inhibitor is selected from pembrolizumab, nivolumab, cemiplimab, atezolizumab, avelumab, durvalumab, or ipilimumab.

37. A pharmaceutical composition according to any one of claims 33 to 36 for use in photodynamic therapy or cytoluminescence therapy.

38. atherosclerosis; multiple sclerosis; diabetes; diabetic retinopathy; arthritis; rheumatoid arthritis; fungal, viral, chlamydial, bacterial, nanobacterial or parasitic infections; HIV; AIDS; infection by SARS virus (preferably Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2)), Asian (Chicken) Influenza virus, Dengue virus, Herpes simplex or Herpes zoster; hepatitis; viral hepatitis; cardiovascular disease; coronary artery stenosis; carotid artery stenosis; intermittent claudication; dermatological conditions; acne; psoriasis; benign or malignant cell hyperproliferation or blood 38. A pharmaceutical composition according to any one of claims 33 to 37 for use in the treatment of a disease characterised by areas of neovascularisation; a benign or malignant tumour; an early stage cancer; cervical dysplasia; soft tissue sarcoma; a germ cell tumour; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin or pancreas.

39. A pharmaceutical composition according to any one of claims 33 to 38 for use in the treatment of diseases characterised by benign or malignant cellular hyperproliferation or by areas of neovascularisation.

40. A pharmaceutical composition according to any one of claims 33 to 39 for use in the treatment of benign or malignant tumors.

41. 41. The pharmaceutical composition of any one of claims 33 to 40 for use in the treatment of early stage cancer; cervical dysplasia; soft tissue sarcoma; germ cell tumor; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin or pancreas.

42. 35. A pharmaceutical composition according to claim 33 or 34 for use in photodynamic diagnosis.

43. The pharmaceutical composition according to any one of claims 33 to 42, wherein the pharmaceutical composition is suitable for administration before the administration of radiation.

44. 44. The pharmaceutical composition of claim 43, wherein the radiation is electromagnetic radiation having a wavelength in the range of 500 nm to 1000 nm.

45. 45. The pharmaceutical composition according to any one of claims 33 to 44, wherein the pharmaceutical composition is in a form suitable for oral, parenteral (including intravenous, subcutaneous, intramuscular, intradermal, intratracheal, intraperitoneal, intratumoral, intraarticular, intraperitoneal, intracranial and epidural), transdermal, airway (aerosol), rectal, vaginal or topical (including buccal, mucosal and sublingual) administration.

46. 46. ​​The pharmaceutical composition of claim 45, wherein the pharmaceutical composition is in a form suitable for oral or parenteral administration.

47. atherosclerosis; multiple sclerosis; diabetes; diabetic retinopathy; arthritis; rheumatoid arthritis; fungal, viral, chlamydial, bacterial, nanobacterial or parasitic infections; HIV; AIDS; infection with SARS virus (preferably Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2)), Asian (avian) influenza virus, dengue virus, herpes simplex or herpes zoster; hepatitis; viral hepatitis; cardiovascular disease; coronary artery stenosis; carotid artery stenosis; intermittent claudication; dermatological conditions; acne; psoriasis; benign or malignant cell hyperproliferation or areas of angiogenesis 34. Use of a compound or complex according to any one of claims 1 to 32 in the manufacture of a medicament for the treatment of diseases characterized by uterine dysplasia, soft tissue sarcoma, germ cell tumors, retinoblastoma, age-related macular degeneration, lymphoma, Hodgkin's lymphoma, head and neck cancer, oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin or pancreas.

48. 33. Use of a compound or complex according to any one of claims 1 to 32 in the manufacture of a phototherapeutic agent for use in photodynamic therapy or cytoluminescence therapy.

49. The phototherapeutic agent may be used to treat a variety of conditions, including but not limited to atherosclerosis; multiple sclerosis; diabetes; diabetic retinopathy; arthritis; rheumatoid arthritis; fungal, viral, chlamydial, bacterial, nanobacterial or parasitic infections; HIV; AIDS; infection by SARS virus (preferably Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2)), Asian (avian) influenza virus, dengue virus, herpes simplex or herpes zoster; hepatitis; viral hepatitis; cardiovascular disease; coronary artery stenosis; carotid artery stenosis; intermittent claudication; dermatological conditions; acne; psoriasis; benign or malignant 49. The use according to claim 48 for the treatment of diseases characterized by areas of hyperproliferation of cells or angiogenesis; benign or malignant tumors; early stage cancers; cervical dysplasia; soft tissue sarcoma; germ cell tumors; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin or pancreas.

50. 50. The use according to any one of claims 47 to 49, wherein the drug or phototherapeutic agent is intended for the treatment of diseases characterized by benign or malignant cellular hyperproliferation or by areas of neovascularization.

51. The use according to any one of claims 47 to 50, wherein the drug or phototherapeutic agent is for the treatment of a benign or malignant tumor.

52. 52. The use of any one of claims 47 to 51, wherein the drug or phototherapy agent is for the treatment of early stage cancer; cervical dysplasia; soft tissue sarcoma; germ cell tumor; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin, or pancreas.

53. 33. Use of a compound or complex according to any one of claims 1 to 32 in the manufacture of a photodiagnostic agent for use in photodynamic diagnosis.

54. The use according to any one of claims 47 to 53, wherein the drug, phototherapeutic agent or photodiagnostic agent is suitable for administration before the administration of radiation.

55. 55. The use according to claim 54, wherein the radiation is electromagnetic radiation having a wavelength in the range of 500 nm to 1000 nm.

56. atherosclerosis; multiple sclerosis; diabetes; diabetic retinopathy; arthritis; rheumatoid arthritis; fungal, viral, chlamydial, bacterial, nanobacterial or parasitic infections; HIV; AIDS; infection with SARS virus (preferably Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2)), Asian (Chicken) Influenza virus, Dengue virus, Herpes simplex or Herpes zoster; hepatitis; viral hepatitis; cardiovascular disease; coronary artery stenosis; carotid artery stenosis; intermittent claudication; dermatological conditions; acne; psoriasis; diseases characterized by areas of benign or malignant cellular hyperproliferation or angiogenesis; benign or malignant diseases 34. A method of treating a cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin or pancreas, said method comprising administering to a human or animal in need thereof a therapeutically effective amount of a compound or complex according to any one of claims 1 to 32.

57. 33. A method for photodynamic or cytoluminescent therapy of a disease in a human or animal, said method comprising administering to a human or animal in need of treatment a therapeutically effective amount of a compound or complex according to any one of claims 1 to 32.

58. The human or animal disease may be atherosclerosis; multiple sclerosis; diabetes; diabetic retinopathy; arthritis; rheumatoid arthritis; fungal, viral, chlamydial, bacterial, nanobacterial or parasitic infection; HIV; AIDS; infection by SARS virus (preferably Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2)), Asian (avian) influenza virus, dengue virus, herpes simplex or herpes zoster; hepatitis; viral hepatitis; cardiovascular disease; coronary artery stenosis; carotid artery stenosis; intermittent claudication; dermatological conditions; acne; psoriasis; benign or a disease characterized by areas of malignant cell hyperproliferation or angiogenesis; a benign or malignant tumor; early stage cancer; cervical dysplasia; soft tissue sarcoma; germ cell tumor; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin, or pancreas.

59. 59. The method of any one of claims 56 to 58, wherein the human or animal disease is characterized by benign or malignant cellular hyperproliferation or by areas of neovascularization.

60. 60. The method of any one of claims 56 to 59, wherein the human or animal disease is a benign or malignant tumor.

61. 61. The method of any one of claims 56 to 60, wherein the human or animal disease is early stage cancer; cervical dysplasia; soft tissue sarcoma; germ cell tumor; retinoblastoma; age-related macular degeneration; lymphoma; Hodgkin's lymphoma; head and neck cancer; oral cancer; or cancer of the blood, prostate, cervix, uterus, vagina or other female adnexa, breast, nasopharynx, trachea, larynx, bronchi, bronchioles, lung, hollow organs, esophagus, stomach, bile duct, intestine, colon, colorectum, rectum, bladder, ureter, kidney, liver, gallbladder, spleen, brain, lymphatic system, bone, skin, or pancreas.

62. 33. A method for the photodynamic diagnosis of disease in humans or animals, said method comprising administering to a human or animal a diagnostically effective amount of a compound or complex according to any one of claims 1 to 32.

63. 63. The method of any one of claims 56 to 62, wherein after administration of the compound or complex of any one of claims 1 to 32, the human or animal is subjected to irradiation.

64. 64. The method of claim 63, wherein the radiation is electromagnetic radiation having a wavelength in the range of 500 nm to 1000 nm.

65. A drug combination or kit comprising: (a) a compound or complex according to any one of claims 1 to 32; (b) a co-agent that is an immune checkpoint inhibitor.

66. 66. The pharmaceutical combination or kit of claim 65, wherein said immune checkpoint inhibitor is selected from pembrolizumab, nivolumab, cemiplimab, atezolizumab, avelumab, durvalumab, or ipilimumab.

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