WO2005033110A1

WO2005033110A1 - Processes for producing polysubstituted phythalocyanines

Info

Publication number: WO2005033110A1
Application number: PCT/CA2004/001790
Authority: WO
Inventors: Clifford Leznoff; Jose Luis Sosa-Sanchez
Original assignee: York University
Priority date: 2003-10-07
Filing date: 2004-10-07
Publication date: 2005-04-14

Abstract

The present invention provides a method for the nucleophilic aromatic substitution of fluorinated phthalocyanines, and phthalocyanine derivatives produced by such method.

Description

PROCESSES FOR PRODUCING POLYSUBSTITUTED PHTHALOCYANINES

BACKGROUND OF THE INVENTION

FIELD OF THE INVENTION

[0001] The present invention relates to processes for producing phthalocyanine compounds and particularly substituted phthalocyanines. More specifically, the present invention provides mono and polysubstituted phthalocyanines.

DESCRIPTION OF THE PRIOR ART

[0002] Phthalocyanines are a group of stable macrocyclic compounds that have important teclinological applications. Phthalocyanines have attracted considerable interest due to their unique properties, which include extremely high thermal stability and chemical resistivity.

Traditionally, phthalocyanines have been used as dyes but recently they have found wide application in fields including liquid crystals, chemical sensors, photodynamic medical therapies, and nonlinear optics.

[0003] The general structure of phthalocyanines is represented by formula I below:

[0004] (I)

[0005] Substituents at the 2,3,9,10,16,17,23, and 24 positions are known as peripheral groups, while substituents at positions 1,4,8,11,15,18,22, and 25 positions are known as non- peripheral groups. The core of the phthalocyanine molecule may be metal-free or may contain any of the metals or oxymetals which are capable of being complexed within the core. Examples of suitable metals are known in the art, such as in US Patent No. 4,824,948 (which is incorporated herein by reference). The basic structure of phthalocyanines allows for different types of chemical functionalization which provides the possibility of obtaining an enormous variety of new phthalocyanine compounds. [0006] However, one limiting aspect of phthalocyanine compounds is their insolubility in common organic solvents and water. As such, one highly desired characteristic of phthalocyanines is that they be soluble. Phthalocyanines possess an extended π-conjugated electron system which permits π stacking (aggregation) between planar macromolecules when such molecules are in close proximity. One strategy that has been used to increase the solubility of phthalocyanines (with valence states higher than two) is axial substitution with bulky ligands (e.g. Sosa-Sanchez et al., J.P.P., 6, 121, (2002) (the contents of which are incorporated herein by reference). However, this type of substitution is not easily achieved due to the fact that not all metals (ligands) are easily displaced. [0007] hi another strategy, it has been found that the addition of certain substituents to the peripheral and non-peripheral positions of the phthalocyanine molecules increases the separation distance between the stacked macromolecules, thereby rendering them more soluble. Such substitution can be accomplished, for example, by condensing a substituted phthalonitrile precursor into a phthalocyanine. In another example, the substituents of pre- formed, easily prepared substituted phthalocyanines are functionalized after addition to the macromolecule. An example of this post-formation functionalization is provided in US Patent No. 4,001,695 (incorporated herein by reference). However, in this patent, the starting phthalocyanine molecule is relatively unreactive and, therefore, stringent conditions are required. A similar shortcoming is found with another process as taught in US Patent No. 4,606,859 (incorporated herein by reference) wherein a method is described for displacing the CI substituents in hexadecachlorophthalocyanines. [0008] Various mono substituted phthalocyanines are known in the art. However, such compounds are typically formed as regioisomers. Thus, another desired characteristic of phthalocyanines is that they are symmetrical. As such, the phthalocyanine structure is preferably polysubstituted. These desired characteristics are discussed further by N. Bhardwaj et al. in Can. J. Chem., 80, 141-147, (2002) (the contents of which are incorporated herein by reference) . [0009] Thus, a new process for obtaining soluble phthalocyanines is desired. SUMMARY OF THE INVENTION [0010] In one embodiment, the present invention provides a method for solubilizing a fluorinated phthalocyanine compound said method comprising the step of: [0011] -providing a nucleophilic species having a nucleophilic site, wherein the nucleophilic site is selected from the group consisting of C, Si, N, P, O, or S atoms; [0012] -reacting the nucleophilic species with the fluorinated phthalocyanine compound, the reaction of the nucleophilic species with the fluorinated phthalocyanine compound producing a soluble substituted phthalocyanine compound substituted at peripheral and non- peripheral sites, the substituted phthalocyanine compound having a general formula [N^subjMPcX_k] wherein: [0013] -Pc is a phthalocyanine general structure; [0014] -M is a nonmetal, a metal, a metal oxide, or a metal halide [0015] -N^sub is a peripheral or non-peripheral substituent which has been covalently bonded to the phthalocyanine (Pc) by means of a nucleophilic substitution reaction; [0016] -X is a halogen atom, which in one aspect is a fluorine atom; further, j and k are integers wherein j ranges between 1 and 16 and k ranges between 0 and 15 wherej+k=16. [0017] In another embodiment, the present invention provides substituted phthalocyanine compounds produced by the above-mentioned method, such compounds having the general formula [N^su _jMPcX_k] wherein: [0018] -Pc is the phthalocyanine general structure; [0019] -M is a nonmetal, a metal, a metal oxide, or a metal halide; [0020] -N^sub is a peripheral or non-peripheral substituent which has been covalently bonded to the phthalocyanine (Pc) by means of a nucleophilic substitution reaction wherein the bonding to the phthalocyanine occurred at a nucleophilic site on the substituent and wherein the nucleophilic site may comprise C, Si, N, P, O, S atoms; [0021] -X is a halogen atom, which in one aspect is a fluorine atom; [0022] -and, j and k are integers wherein j ranges between 1 and 16 and k ranges between 0 and 15 where j+k=l 6.

BRIEF DESCRIPTION OF THE DRAWINGS [0023] These and other features of the preferred embodiments of the invention will become more apparent in the following detailed description in which reference is made to the appended drawing wherein: [0024] Figure 1 depicts a reaction scheme according to one aspect of the method of the present invention. [0025] Figure 2 depicts a summary of a general reaction scheme for the synthesis of polysubstituted phthalocyanines using preferred nucleophiles. [0026] Figure 3 depicts a reaction scheme for the synthesis of tridecafluoro- tri(octanethio)-phtlialocyaninatozinc(II). [0027] Figure 4 depicts a reaction scheme for the synthesis of decafluoro- hexapyrrolidino-phthalocyaninatocobalt(II). [0028] Figure 5 depicts a reaction scheme for the synthesis of pentafluoro- tetramorpholino-tripyπOlidino-phthalocyaninatocobalt(π). [0029] Figure 6 depicts a reaction scheme for the synthesis of decafluoro- hexamo holino-phthalocyaninatocobalt(II) . [0030] Figure 7 depicts reaction schemes for the synthesis of tetradecafluoro- di(propylamino)-phthalocyaninatocobalt(II), dodecafluoro-tetrapyrrolidino- phthalocyaninatocobalt(II) and mono-(5-ethyl-l,3-dioxane-5-methyloxy)-hexafluoro- tetraneopentoxy-pentapyrrolidino-phthalocyaninatocobalt(II). [0031] Figure 8 depicts a reaction scheme for the synthesis of hexacyclohexylamino- decafluoro-phthalocyaninatocobalt(II) . [0032] Figure 9 depicts a reaction scheme for the synthesis of pentacyclohexylamino- nonafluoro-phthalocyaninatozinc(II) . [0033] Figure 10 depicts a reaction scheme for the synthesis of trianilino-tridecafluoro- phthalocyaninatocobalt(II). [0034] Figure 11 depicts a reaction scheme for the synthesis of tetraanilino-dodecafluoro- phthalocyaninatozinc(H). [0035] Figure 12 depicts a reaction scheme for the synthesis of nonafluoro-heptapyrrolo- phthalocyaninatozinc(II). [0036] Figure 13 depicts a reaction scheme for the synthesis of the product of imidazole and hexadecafluorophthalocyaninatocobalt(II). [0037] Figure 14 depicts a reaction scheme for the synthesis of tridecaflouro- monomoφholino-di(propylamino)-phthalocyaninatozinc(II). [0038] Figure 15 depicts a reaction scheme for the synthesis of dodecafluoro- monomorpholino-dipropylamino-monopyrrolidino-phthalocyaninatozinc(II). [0039] Figure 16 depicts a reaction scheme for the synthesis of tetraanilino-di(3,3- dimethylbutanoxy)-decafluoro-phthalocyaninatozinc(II) . [0040] Figure 17 depicts a reaction scheme for the synthesis of tetra(cyclohexylamino)- mono(3,3-dimethylbutanoxy)-undecafluoro-phthalocyaninatozinc(II). [0041] Figure 18 depicts a reaction scheme for the synthesis of tri-(3,3- dimethylbutanoxy)-heptafluoro-hexapyrrolidino-phthalocyaninatozinc(H). [0042] Figure 19 depicts a reaction scheme for the synthesis of penta(cyclohexylamino)- mono(5-ethyl-l,3-dioxane-5-methyloxy)-decafluoro-phthalocyaninatozinc(π). [0043] Figure 20 depicts a reaction scheme for the synthesis of penta(cyclohexylamino)- mono(5 -ethyl- 1 ,3-dioxane-5-methyloxy)-decafluoro-phthalocyaninatozinc(II). [0044] Figure 21 depicts a reaction scheme for the synthesis of tetra(cyclohexylamine)- tetra(cyclohexylmethoxy)-octafluoro-phthalocyaninatozinc(II). [0045] Figure 22 depicts a reaction scheme for the synthesis of tri(3,3- dimethylbutanoxy)-octafluoro-pentamorpholino-phthalocyaninatozinc(II) . [0046] Figure 23 depicts a reaction scheme for the synthesis of tetra(cyclohexyloxy)- octafluoro-tetramorpholino-phthalocyaninatozinc(II). [0047] Figure 24 depicts a reaction scheme for the synthesis of tetra(cyclohexylmethyloxy)-di(cyclopentylamino)-mono(3,3-dimethylbutanoxy)-nonafluoro- phthalocyaninatozinc(II) [0048] Figure 25 depicts a reaction scheme for the synthesis of di(cyclohexylmethyloxy)- mono(cyclohexyloxy)-tetra(cyclopentylamino)-nonafluoro-phthalocyaninatozinc(π). [0049] Figure 26 depicts a reaction scheme for the synthesis of octafluoro-octa(l- octanyloxy)-phthalocyaninatozinc(II) . [0050] Figure 27 depicts a reaction scheme for the synthesis of tetrafluoro- dodeca(cyclohexylmethyloxy)-phthalocyaninatozinc(II) .

DESCRIPTION OF THE PREFERRED EMBODIMENTS [0051] The term "nucleophile" is recognized in the art, and as used herein means a chemical moiety having a reactive pair of electrons. Examples of nucleophiles include uncharged compounds such as amines, mercaptans, thiols, and alcohols, and charged moieties such as alkoxides, thiolates, carbanions, and a variety of organic and inorganic anions. Illustrative anionic nucleophiles include simple anions such as hydroxide, azide, cyanide, thiocyanate, acetate, formate or chloro formate, and bisulfite. Organometallic reagents such as organocuprates, organozincs, organolithiums, Grignard reagents, enolates, acetylides, and the like may, under appropriate reaction conditions (as known in the art, and as illustrated further below) be suitable nucleophiles. [0052] In one embodiment, the present invention provides a process for the bonding of desired substituents to known, commercially available phthalocyanine molecules through a nucleophilic substitution reaction. Some known phthalocyanines, as described above, require specific, often stringent conditions for displacing substituents. This is the case, for example, with hexadecachlorophthalocyanine, which is known to be highly insoluble. The process of the present invention allows for the preparation of soluble phthalocyanine derivatives whereby fluorinated phthalocyanines, for example hexadecafluorophthalocyanines, undergo direct nucleophilic aromatic substitution reactions in order to yield phthalocyanine derivatives characterized by increased solubility. [0053] The process of the present invention can be used to produce phthalocyanine derivatives of fluorinated phthalocyanines having the general formula [N^subMPcX_k] wherein: [0054] -Pc is the phthalocyanine general structure. [0055] -M is a nonmetal, a metal, a metal oxide, or a metal halide. The term "nonmetal" as used herein means atoms other than metal atoms such as, for example, two hydrogen atoms. Typical examples of the metal include, iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Typical examples of the metal oxide include, titanyl and vanadyl. Typical examples of the metal halide include, aluminum chloride, indium chloride, germanium chloride, tin(ll) chloride, tin(IV) chloride, and silicon chloride. [0056] -N^su is a peripheral or non-peripheral substituent which has been covalently bonded to the phthalocyanine (Pc) by means of a nucleophilic substitution reaction wherein the bonding to the phthalocyanine occurred at a nucleophilic site on the substituent and wherein the nucleophilic site may comprise C, Si, N, P, O, S atoms. [0057] -X is a halogen atom, which in one aspect is a fluorine atom; [0058] -further, j and k are integers wherein j ranges between 1 and 16 and k ranges between 0 and 15 where j+k=16. [0059] In general, depending on the steric effect: j = 1, 2, 3... 16 for N^sub with low steric effect. j = 1, 2, 3 ... 13 for N^su with high steric effect. [0060] When large nucleophile molecules, for example nucleophiles having highly branched structures, are used in the method of the present invention, substitution of a fluorinated phthalocyanine may generally occur at between 1 and 13 of the peripheral and/or non-peripheral sites. However, when small or medium sized nucleophile molecules are used in the method of the present invention, substitution of a fluorinated phthalocyanine may occur at between 1 and 16 of the peripheral and/or non-peripheral sites. It may be possible, however, by lengthening reaction times and increasing temperatures, to substitute up to 16 large nucleophile groups onto a phthalocyanine nucleus. [0061] In general, the method of the present invention comprises the step of: [0062] -combining a fluorinated phthalocyanine compound with a nucleophilic species; [0063] -conducting an aromatic nucleophilic substitution reaction of the fluorinated phthalocyanine compound with the nucleophilic species in an appropriate solvent to produce a soluble substituted phthalocyanine derivative. [0064] The nucleophilic substitution method of the present invention is characterized by the ability to produce fully or partially substituted derivatives of fluorinated phthalocyanines having improved solubility. [0065] As stated above, the phthalocyanine derivatives of the present invention comprise between 1 and 16 substituted groups, wherein any unsubstituted groups are fluoro groups. In general, the greater the number of substituted groups, the higher the solubility of the final product. In one aspect of the present invention more than one type of nucleophile is used, as illustrated by the examples below, in order to produce derivatives of fluorinated phthalocyanines having two or more different substituent groups. When different nucleophiles are used, separate reactions are sequentially carried out, wherein each reaction is controlled to limit substitution. [0066] The amount of substitution which occurs can be controlled by varying the reaction times and temperatures. The temperature at which the nucleophilic substitution reaction proceeds, and the time of the reaction, will vary depending on the nucleophile used, and the extent of substitution that is desired. [0067] In addition, an excess of nucleophile can be used in order to maximize the reaction rates between reactants, and the degree of substitution of the product. [0068] The method of the present invention allows for the synthesis of derivatives of fluorinated phthalocyanines that are substituted at one or more peripheral and non-peripheral sites and which cannot be easily obtained by methods known in the art. [0069] The core of the phthalocyanine nucleus may be metal-free or may contain any metal or oxymetal that is capable of being complexed to the core of phthalocyanines. Examples of such metals include, but are not limited to, zinc, cobalt, copper, nickel, magnesium, palladium, gallanyl, vanadyl, germanium, indium, lead, manganese, iron, and cadmium. The core of the phthalocyanine may also be occupied by non-metal moieties, such as 2 H atoms. [0070] Nucleophiles having a nucleophilic site comprising a C, Si, N, P, O, or S atom may be utilized in the substitution reactions of the present invention. [0071] Examples of potential nucleophiles used in the present invention include, but are not be limited to, electron rich groups such as: :OH^", :OR^", C₂ to C ₀ alkynl groups including C₂, C₃, C₄, C₅, C₆, C₇, C₈, C , C₁₀, Cπ, C₁₂, C₁ , C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁₉, and C ₀ alkynl groups, :CN^", RCOO:^", :NH₃, :NHRR', :SH^", :P(C₆H₅)₃ , alcohols, sterols, and :SR^". In the above list, R or R' may be a substituted or un-substituted, linear or branched, to C ₀ alkyl group including C_\, C₂, C₃, C , C₅, C₆, C₇, C₈, C₉, C₁₀, Cπ, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁ , and C ₀ alkyl groups, a substituted or un-substituted, linear or branched C\ to C₂₀ alkoxy group including , C₂, C₃, C , C₅, C₆, C₇, C₈, C , C₁₀, Cπ, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁ , and C₂₀ alkoxy groups, and an aryl or heteroaryl group. [0072] Examples of aryl or heteroaryl groups include, but are not limited to, phenyl, naphthyl, thienyl, furyl, pyrryl, thiazolyl, isothiazolyl, quinolyl, indolyl, pyridyl, benzoimidazolyl and benzothiazolyl, which optionally contain substituents. Where R is phenyl the substituents may be situated in the ortho, meta and/or para positions. Preferred substituents are selected from C _{1- 0} -alkyl, including C , C₃, C₄, C₅, C₆, C , C₈, C , C₁₀, Cπ, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁₉, and C₂₀ alkyl groups; C _1-20 -alkoxy including , C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, Cio, Cπ, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁ , C₁₈, C₁ , and C₂₀ alkoxy groups, S- C _1- o -alkyl; aryl, for example, phenyl; S-aryl, halogen; nitro; cyano; tertiary amino, such as di-N-alkyl-, N-alkyl-N-aryl- and di-N-aryl-amino; -COOH and acyl and acylamino. Individuals skilled in the art will recognize other groups having the desired nucleophilic site. [0073] An example of a sterol that may be used as a nucleophile in the method of the present invention is cholesterol. [0074] Examples of specific alkoxide nucleophiles that can be used in the method of the present invention include, but are not limited to, neopentoxide, methoxide, ethoxide, propoxide, isopropoxide, butanoxide, pentanoxide, and cyclohexanoxide. [0075] Examples of specific amine nucleophiles that can be used in the method of the present invention include, but are not limited to, morpholine, piperidine, and pyrrolidine. [0076] Examples of primary amine nucleophiles that can be used in the method of the present invention include, but are not limited to, propylamine, cyclohexamine, and cyclopentylamine. [0077] Examples of specific carbon nucleophiles that can be used in the method of the present invention include, but are not limited to, cyanide, acetylide, methyl acetylide, phenyl acetylide, the anion from malononitrile, and any anion alpha to a carbonyl group. [0078] Examples of specific phenoxides that can be used in the method of the present invention include, but are not limited to, p-tert-butylphenoxide, phenoxide, o-, m-, and p- halosubstituted phenoxides, o-, m-, p-alkyl and alkoxyphenoxides, o-, m-, and p-amino or thiophenoxides, also naphthoxides and other polynuclear aromatic alkoxides. [0079] Examples of specific thiols that can be used in the method of the present invention include, but are not limited to, 1-octanethiol, methyl thiol, ethyl thiol propyl thiol, and butyl thiol. Salts of aromatic thiols such as phenyl thiol and substituted aromatic thiols can also be used as the nucleophile. [0080] Examples of specific alcohols that can be used in the method of the present invention include, but are not limited to, cyclohexanol, cyclohexylmethanol, 3,3- dimethylbutanol, neopentylalcohol, and 5-ethyl-l,3 dioxane-5 -methanol. [0081] The chemical nature of the nucleophilic reagents can be used to alter the physical properties of the phthalocyanine products, particularly their solubility, for example increasing solubility. [0082] Figure 1 illustrates a reaction scheme according to one aspect of the present invention. The reaction scheme depicted in figure 1 is only an example of the method of the present invention and, as such, the present invention is not limited to this example. As can be seen in this aspect, the method involves reaction of a fluorinated phthalocyanine 10 (e.g. F₁₆MPc wherein M is a nonmetal, a metal, a metal oxide, or a metal halide) with a nucleophile 20. In figure 1, the nucleophile is designated as X, XH, or RX, wherein X may be a C, Si, O, F, CI, Br, I, CN, N, or S atom, and R is an alkyl or aryl group. A nucleophilic substitution reaction 30 between the phthalocyanine 10 and nucleophile 20 results in the synthesis of a phthalocyanine derivative 40 that is substituted at one or more peripheral and/or non-peripheral sites. For example, substitution may occur at one, two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, or sixteen of the peripheral and/or non-peripheral sites. [0083] General summaries of methods of the present invention that have proved to be successful in obtaining phthalocyanine compounds mono- or polysubstituted by a nucleophilic substitution reaction are as provided by example below. [0084] In one aspect, the method of the present invention also comprises a step of activating the nucleophilic species using a strong base, such as n-butyllithium, in a non-polar organic solvent. Examples of solvents that can be used in this embodiment of the present method include, but are not limited to, diglyme, tetrahydrofuran (THF), diethyl ether, dioxane, glyme, triglyme and tetraglyme. In this aspect of the present invention, the nucleophile that is used cannot react directly with the fluorinated phthalocyanine. In this aspect of the present invention, the nucleophile must first be activated so that it may undergo a nucleophilic substitution reaction, prior to reaction with the fluorinated phthalocyanine. Examples of nucleophiles that require activation include, but are not limited to, cyclohexylmethanol, cyclohexanol, 3,3 dimethylbutanol, and 5-ethyl-l,3-dioxane-5- methanol. Activation of a nucleophile may be accomplished, for example, by reaction of the nucleophile with a strong base, such as n-butyllithium in a non-polar organic solvent. If a strong base is used, activation of the nucleophile occurs through deprotonation of the nucleophile, creating a more nucleophilic anion (e.g. ROH to RO-). In one aspect, activation refers to the act of converting an unreactive compound, such as alcohol or phenol, into a compound which may act as a nucleophile (eg. an active metal alkoxide). Subsequent to the activation of the nucleophile, an amount of fluorinated phthalocyanine is added to the activated nucleophile mixture. [0085] The temperature at which the nucleophilic substitution reaction proceeds, and the time of the reaction, will vary depending on the nucleophile used, and the extent of substitution that is desired. [0086] In an alternate aspect of the present invention, a nucleophile may be used that does not require activation prior to reaction with a fluorinated phthalocyanine. In this embodiment, the nucleophile is reactive enough to react directly with the fluorinated phthalocyanine and, as such, the activation step can be skipped. The fluorinated phthalocyanine starting material may react with a solution of the nucleophile in the appropriate solvent. [0087] Certain nucleophile reagents are liquid at room temperature and, as such, in one aspect of the present invention the nucleophile in a liquid state may react with the phthalocyanine directly. In this aspect of the present invention, the solvent itself can serve as the source of the nucleophile. For example, morpholine, propylamine, pyrrolidine, pentylamine, and hexylamine may serve as both solvent and the nucleophile. These compounds are examples, which are not limited to, more reactive nucleophiles. The temperature at which the nucleophilic substitution reaction proceeds, and the time of the reaction, will vary depending on the nucleophile used, and the extent of substitution that is desired. [0088] In an alternate aspect of the method of the present invention, an ionic compound may be used as a nucleophile in an aprotic solvent. Examples of aprotic solvents include, but are not limited to, acetone and ethyl acetate. In this embodiment, a catalyst, for example a cyclic polyether catalyst, is used to activate the nucleophilic species as a naked anion. After activation, the nucleophile may then be reacted with a fluorinated phthalocyanine. [0089] Figure 2 depicts a summary of a general reaction scheme for one aspect of the synthesis of polysubstituted phthalocyanines through nucleophilic substitution reaction. A nucleophilic substitution reaction 30 between the fluorinated phthalocyanine 10 and any one of the nucleophiles 50 to 63 results in the synthesis of a phthalocyanine derivative 40 that is substituted at one or more peripheral and/or non-peripheral sites. For example, substitution may occur at one, two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, or sixteen of the peripheral and/or non-peripheral sites, hi this aspect, M is cobalt or zinc. [0090] Upon completion of the nucleophilic substitution of the fluorinated phthalocyanine, crude product may be obtained by extraction with an organic solvent or evaporation of the solvent from an aqueous mixture. The final products may be isolated after column chromatography using silica gel and an eluent that depends on the nature of the substituents on the fluorinated phthalocyanine derivative. An individual of skill in the art will, however, recognize alternate methods that may be used for the isolation of the crude product and the final product. [0091] In one embodiment, the present invention provides soluble phthalocyanine derivatives produced by the method described above, such derivatives having a general formula [N^subMPcX_k] wherein: [0092] -Pc is the phthalocyanine general structure. [0093] -M is a nonmetal, a metal, a metal oxide, or a metal halide. The term "nonmetal" as used herein means atoms other than metal atoms such as, for example, two hydrogen atoms. Typical examples of the metal include, iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Typical examples of the metal oxide include, titanyl and vanadyl. Typical examples of the metal halide include, aluminum chloride, indium chloride, germanium chloride, tin(ll) chloride, tin(lN) chloride, and silicon chloride. [0094] -N^sub is a peripheral or non-peripheral substituent which has been covalently bonded to the phthalocyanine (Pc) by means of a nucleophilic substitution reaction wherein the bonding to the phthalocyanine occurred at a nucleophilic site on the substituent and wherein the nucleophilic site may comprise C, Si, N, P, O, S atoms. [0095] -X is a halogen atom, which in one aspect is a fluorine atom. [0096] -Further, j and k are integers wherein j ranges between 1 and 16 and k ranges between 0 and 15 where j+k=l 6. [0097] An individual skilled in the art will recognize uses for the phthalocyanine derivatives of the present invention including, but not limited to, use in optical limiting devices to block near LR radiation and optical recording materials for direct-read-after- write devices, use as photothermal converting agents, use as pigments, and use in heat ray shielding films. [0098] The examples provided below are for illustration only and are not intended to limit the scope of the present invention. MALDI-MS was used to characterize the products of the reactions in the examples in terms of the products' atomic mass units. Tables 1 to 4 present the spectroscopic data for examples 1 to 4 respectively. [0099] Although all the examples below are conducted under an argon atmosphere, any other common inert gas may be used. Examples of other suitable inert gases include, but are not limited to, nitrogen, helium, and neon. Argon and nitrogen are preferred. Although it is possible to conduct the method of the present invention in air, side products may be formed by the reaction of moisture or oxygen with the reactants and products. As such, it is preferable to carry out the reaction under an inert gas. [00100] All publications, patents and patent applications mentioned in this application are herein incorporated by reference in their entirety to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference in its entirety. Examples: Nucleophilic Substitution of Fluorinated Phthalocyanines [00101] Example 1: Synthesis of tetrafluorododecaneopentoxyphthalocyanine zinc [00102] In a 100 ml Schlenk type flask fitted with a condenser, 40 ml of diglyme were placed under an argon atmosphere. Then 81 lmg (9.2 mmol) of neopentyl alcohol were introduced while the solution was stirred. When all the alcohol has dissolved, 4.3 ml of a 1.6 M solution of n-BuLi in hexane were added under an argon stream. Later on, 20 mg (0.023 mmol) of F₁₆ZnPc were added and heating is provided to get the reaction mixture to a temperature of 110-130°C. The reaction is allowed to proceed for 8 hr. and then heating is discontinued. When the reaction mixture was cooled to room temperature it is poured into 350 ml of distilled water. After adding some acidified water to achieve neutrality, a green precipitate is recovered by filtration. The product is isolated after purification using a wet column, packed with silica gel, and a mixture of hexanes/ethyl acetate (7:3) as eluent. Product yield is 53% based on dodecasubstituted product. [00103] Example 2: Synthesis of octafluorooctamorpholinephthalocyanine zinc [00104] hi a 100 ml Schlenk type flask fitted with a condenser, 40 ml of morpholine and 20 mg of F₁₆ZnPc (0.023 mmol) were placed under an argon atmosphere. After most of the Pc material has dissolved, 0.805 ml of morpholine (9.24 mmol) were added and heating is provided to get to a temperature of 110-120°C. The reaction mixture is kept at this temperature under stirring for about 5-8 hr. The work up to isolate the product is similar to that of example one, the only difference being the eluting mixture which in this case is a mixture of CH₂C1₂ and methanol (10:1). The yield obtained in this case was 53% based on the octasubstituted product. [00105] Example 3: Synthesis of diβuorotetradecacyanophthalocyanine zinc [00106] In a 100 ml Schlenk type flask, fitted with a condenser, 40 ml of acetonitrile and 150 mg of KCN (2.3 mmol) were placed under an argon atmosphere. Then 20 mg of F₁₆ZnPc (0.023 mmol) and 4 mg of 18-crown-6 (0.016 mmol) were added under the same argon atmosphere. Heating is provided and reaction temperature was kept under reflux for 20 hr. When the reaction mixture gets to room temperature solvent is evaporated and the recovered green solid is rinsed with hot water (3x 150 ml). The final product is isolated after purification using a wet chromatographic column packed with silica-gel 60 and a mixture of CH₂C1₂/ methanol (1 : 1) with a 27% yield based on the tetradecasubstituted product. [00107] Example 4: Synthesis oftetrafluorododeca-4-tertbutylphenoxyphthalocyanine zinc [00108] In a 100 ml Schlenk type flask fitted with a condenser, 40 ml of diglyme were introduced under an argon atmosphere. Then 690 mg of 4-tertbutylphenol were added and stirring was provided to dissolve it completely. Na metal (90 mg) were added and heating was provided to start the reaction. After approximately 4-5 hr, when all Na metal had dissolved 10 mg of F₁₆ZnPc were introduced at room temperature under an argon current. The reaction is allowed to proceed for 8 hr at 95-105°C and then, after cooling the reaction mixture to room temperature, it was poured into 350 ml of distilled water. Some acidified water was added to get a neutral solution and the precipitate, a green solid, was recovered by filtration. The product was isolated after purification using a wet column packed with silica gel, and a mixture of hexanes/ethyl acetate (7:3) as eluent. The yield was 48% based on a dodecasubstituted product. [00109] Example 5: Synthesis ofhexadeca-1-octanethiophthalocyanine zinc [00110] In a 100 ml Schlenk type flask fitted with a condenser, 40 ml of diglyme and 1.7 ml of octanethiol were introduced under an argon atmosphere. Then 218 mg of Na (metal) were added under the same conditions as before and heat was provided . After all sodium had dissolved 25 mg of F₁₆ZnPc were added at room temperature. Heating was provided again and the reaction was allowed to proceed at 95-110°C for about 16 hr. When the reaction mixture was cooled to room temperature it was poured into 350 ml of water and then ethyl ether was used to extract a dark olive green product. Evaporation of the solvent gave an olive-green oil which was further purified by column chromatography using silica-gel and a mixture of toluene/ethyl acetate (30:1) as eluent. The yield was 89% based on a hexadecasubstituted product. [00111] Example 6 Synthesis ofnonafluoroheptaneopentoxyphthalocyanine zinc [00112] In a 100 ml Schlenk type flask fitted with a condenser, 50 ml of dry tetrahydrofuran and 612 mg. (6.9 mmol) of neopentyl alcohol were placed under an argon atmosphere. Then 4 ml of n-butyl lithium (1.6 M in hexanes) were added dropwise under the same conditions. Stirring was provided for 5 minutes to complete the activation of the nucleophile and later on 20 mg. (0.023 mmol) of F₁₆ZnPc were put into the reaction mixture. Heating was provided to get to reflux temperature and reaction was allowed to proceed for 5 hr. Work up to isolate product was similar to that given in example 1. The yield was 63 % based on nonasubstituted product. [00113] Examples 7 to 32 [00114] The following examples all utilize the general procedure described below. [00115] In a 10 ml round-bottom flask, provided with a condenser, 10-20 mg of a phthalocyanine and 2-3 ml of nucleophile (thiol, alcohol or amine) was mixed and stirred under an argon atmosphere. Temperatures and times used in each reaction are detailed in the examples provided below. After finishing the reaction, the nucleophile was removed (either by evaporation or by purification using flash silica gel) and the remaining solid was analysed by MALDI mass spectroscopy. [00116] Example 7 Synthesis of Tridecafluoro-tri(octanethio)-phthalocyamnatozinc(II) (1) [00117] F₁₆ZnPc (10 mg, dried before) and 8.5 ml of 1-octanethiol were heated to 200°C for 17 hrs (on oil bath). The reaction mixture turned from blue to olive green. After distilling it under reduced pressure at 160°C, some of the liquid could be removed but the residue was still liquid. Chromatography on silica gel column on this green liquid using toluene: ethyl acetate = 25 : 1 as eluent, gave three different (liquid) fractions which were analysed by MALDI-MS. The first fraction (green) was characterized by a series of ions indicating that 1- 5 fluorines were replaced by the thiol. The peaks in the second fraction (brown) don't match with the molecular weights of any substituted products. The third fraction (green) shows a series of ions where 3, 4, 5, 11, 12 or 13 fluorines are replaced by the thiol. The reaction scheme for the synthesis of this product is provided in Figure 3. [00118] Example 8 Synthesis ofDecafluoro-hexapyrrolidino-phthalocyaninatocobalt(II) (2) [00119] F₁₆CoPc (30 mg) in 5 ml 1-octanol were heated to 200°C for 21 hrs. The reaction mixture was transferred to test tubes. Precipitation was achieved by addition of ethanol. The precipitate was collected by centrifugation and washed twice with methanol. After evaporating the solvent, an aliquot was taken for MALDI-MS. (No reaction took place at this step according to MALDI-MS.) Pyrrolidine (1 ml) was added to the rest of the solid and the mixture was heated to 40-80°C for 30 min. Colour change from blue to olive green could be seen. Then the pyrrolidine was evaporated and an aliquot taken for MALDI-MS. This time a replacement of 4-6 fluorines took place. To the rest 1 ml of morpholine was added and the mixture was heated to 140°C for 20 hrs. The colour changed to blackish green. After precipitating into water and filtering, a black solid remained, which was submitted for MALDI-MS. No reasonable products could be identified for this last step. The reaction scheme for the synthesis of this product is provided in Figure 4. [00120] Example 9: Synthesis ofUndecafluoro-pentapyrrolidino- phthalocyaninatocobalt(II) [00121] 30 mg of F₁₆CoPc were dissolved in 5 ml of 1-octanol and heated to 200°C for 19 hrs. An aliquot was taken for MALDI-MS, which shows no evidence of reaction. Pyrrolidine (1 ml) was added to the mixture (without removing the 1-octanol) and heated to 100°C for 1 h. The colour changed from blue to green. The pyrrolidine was evaporated and an aliquot taken for MALDI-MS, which shows replacement of 4-6 fluorines by pyrrolidine. To the remaining mixture, 1 ml of morpholine was added and heated to 140°C for 19 hrs. The colour turned to very dark (brown black purple). The mixture was precipitated into ethanol, then centrifuged. After washing twice with methanol the blackish green solid was submitted for MALDI-MS, which shows no reasonable products. [00122] Example 10: Synthesis ofPentafluoro-tetramorpholino-tripyrrolidino- phthalocyaninatocobalt(II) [00123] F₁₆CoPc (30 mg) and 2 ml of pyrrolidine were mixed at 0°C and stirred for 30 min. The colour changed from blue green to green. An aliquot was taken and submitted for MALDI-MS after evaporating the pyrrolidine. It shows replacement of 4-6 fluorines by pyrrolidine. The remaining mixture was now stirred at room temperature for another 30 min. No further reaction took place at this step according to MALDI-MS. After heating the mixture to 50°C for 30 min the MALDI-MS shows substitution of 4-7 fluorines. After heating to 90°C for another 30 min, only the 5-7 substituted products were left. The mixture was olive green now. Then pyrrolidine was evaporated and 1 ml of morpholine was added. The mixture was stirred at room temperature for 30 min. It turned darker. An aliquot was submitted for MALDI-MS. It shows the following substitution pattern:

centrifuged, filtered and dried. The MALDI-MS shows the following substitution pattern:

the synthesis of this product is provided in Figure 5. [00126] Example 11: Synthesis ofDecafluoro-hexamorpholino-phthalocyaninatocobalt(II) [00127] F₁₆CoPc (20 mg) was dissolved in 2 ml of morpholine and stirred at room temperature for 17 hrs. An aliquot was taken, precipitated into water, centrifuged and washed twice with water. The MALDI-MS shows that 3-5 fluorines were replaced by morpholine. The remaining mixture was heated to 50-70°C for 2 hrs. An aliquot was taken and worked up in the same way as before. The MALDI-MS shows the replacement of 4-6 fluorines. The remaining mixture was heated to 80°C for 3 hrs and then worked up in the same way. The MALDI-MS shows the replacement of 4-7 fluorines. The reaction scheme for the synthesis of this product is provided in Figure 6. [00128] Example 12: Synthesis ofTetradecafluoro-di(propylamino)- phthalocyaninatocobalt(II), Dodecafluoro-tetrapyιrolidino-phthalocyaninatocobalt(II) and Mono-(5-ethyl-l,3-dioxane-5-methyloxy)-hexafluoro-tetraneopentoxy-pentapyrrolidino- phthalocyaninatocobalt(II) [00129] Fι₆CoPc (40 mg) was dissolved in 1 ml of propylamine and stirred for 10 min. Then the amine was evaporated and an aliquot was taken for MALDI-MS. It shows substitution of 1-6 fluorines by propylamine. To the remaining solid 1 ml of pyrrolidine was added and the suspension was stirred at room temperature for 5 min. After that the pyrrolidine was evaporated and an aliquot was taken for MALDI-MS. It shows substitution of 3-4 fluorines by pyrrolidine but no more products with propylamine as the substituent. To the remaining solid 1 ml of diisopropylamine was added and the mixture was heated to 80°C for 4 hrs. The amine was evaporated and an aliquot taken for MALDI-MS. It shows substitution of 3-5 fluorines by pyrrolidine. There is no evidence that diisopropylamine has reacted with the Pc. To the remaining solid (dark blue green) was added a mixture of 0.93 ml nBuLi and 328 mg neopentylalcohol. The mixture was stirred at 110°C for 90 min. Since the suspension almost solidified, some 5-ethyl-l,3-dioxane-5-methanol was added and heated to 140°C for 1 h. The colour turned from green to brown. But after cooling down it was green again. So another 328 mg neopentylalcohol were added and heated to 140°C for 90 min. The colour turned brown again. The mixture was purified by silica gel chromatography with ethylacetate/hexanes (1 : 1) as the eluent. An olive green and a green fraction were taken and submitted for MALDI-MS. Two peaks among several could be identified: [00130] 1) fluorines were replaced by 5 pyrrolidines and 4 neopentylalcohols [00131] 2) the same as above with an 5-ethyl-l,3-dioxane-5-methanoxy. [00132] The reaction schemes for the synthesis of the various products of this example are provided in Figure 7. [00133] Example 13: Synthesis ofHexacyclohexylamino-decafluoro- phthalocyaninatocobalt(II) [00134] F₁₆CoPc (20 mg) was mixed with 1-2 ml of cyclohexylamme and stirred at room temperature for 2 hrs. An aliquot was taken and purified by chromatography using THF as eluent. Two blue fractions were obtained. The first one shows substitution of 1-6 fluorines. The second one is the starting material. The remaining mixture was heated to 140°C for 2.5 hrs. One green fraction was obtained by using THF as the eluent. The spectra shows substitution of 5-6 fluorines by cyclohexylamme. The reaction scheme for the synthesis of this product is provided in Figure 8. [00135] Example 14: Synthesis ofPentacyclohexylamino-nonafluoro- phthalocyaninatozinc(II) [00136] F₁₆ZnPc (12 mg) was mixed with 1-2 ml of cyclohexylamme and stirred at room temperature for 2 hrs. The solution turned from blue to green. An aliquot was taken and purified by chromatography using ethyl acetate as the eluent. The MALDI-MS is of quite a poor quality, and thus could not be analysed properly. The remaining reaction mixture was then heated to 100°C for 1 h, then purified in the same way. The MALDI-MS shows substitution of 3-6 fluorines by cyclohexylamme. The reaction scheme for the synthesis of this product is provided in Figure 9. [00137] Example 15: Synthesis ofTrianilino-tridecafluoro-phthalocyaninatocobalt(II) [00138] F₁₆CoPc (20 mg) was mixed with 1-2 ml of aniline and stirred at room temperature for 24 hrs. An aliquot was taken and purified by chromatography using THF as eluent. The MALDI-MS shows only low M.W. peaks (<750 m/z). Not even the starting material can be seen. The remaining mixture was heated to 190°C over night. Unfortunately the oil got burnt, so that no exact temperature can be given. The mixture was purified in the same way as the aliquot. The MALDI-MS shows substitution of 1-5 fluorines by aniline. The reaction scheme for the synthesis of this product is provided in Figure 10. [00139] Example 16: Synthesis ofTetraanilino-dodecafluoro-phthalocyaninatozinc(II) [00140] To compare the CoPc and the ZnPc 12 mg of F₁₆ZnPc were dissolved in 1-2 ml of aniline and heated to 200°C for 2 hrs. The colour turned from green to olive green. An aliquot was taken and purified by chromatography using ethyl acetate as eluent. A green and a blue fraction were obtained. Substitution of 3-7 fluorines by aniline was observed. The remaining mixture was heated to 200°C for 4 more hours until the colour changed to very dark. A blue fraction was eluted by chromatography with ethyl acetate as the eluent. The MALDI-MS on this fraction was of poor quality and could not be analysed. [00141] The reaction scheme for the synthesis of this product is provided in Figure 11. [00142] Example 17: Synthesis ofNonafluoro-heptapyrrolo-phthalocyaninatozinc(II) [00143] One spatula tip of potassium hydride was dissolved in freshly distilled pyrrol (1-2 ml) in a small flask under argon at room temperature. After 15 minutes it forms a yellow solution with some white solid. To this mixture were added 10 mg of F₁₆CoPc and then stirred for 3 hrs at room temperature. The resulting green solution was purified by silica gel chromatography using THF as the eluting solvent. The MALDI-MS shows substitution of 5 to 10 fluorines by pyrrole. (This reaction must be handled very cautiously because it can decompose even at room temperature if left for too long. But sometimes it needs a little heat to react. Watching the colour is the best way to control this reaction. It has to change from blue to green.) [00144] The reaction scheme for the synthesis of this product is provided in Figure 12. [00145] Example 18: Synthesis of the product ofimidazole and hexadecafluoroPc II cobalt [00146] Imidazole (70 mg) and sodium hydride (15 mg) were dissolved in 1-octanol and stirred for 15 minutes at room temperature. Then 10 mg of F₁₆CoPc was added and the mixture was heated to 80°C for 20 hrs. The resulting green material was purified by silica gel chromatography using ethyl acetate as the eluting solvent. The MALDI-MS shows that a dimer was formed: two Pc molecules were bound together by coordinating to one imidazole molecule as a common ligand. Further, there is a substitution of 6 to 9 fluorines by imidazole on both Pcs together (probably 3 to 5 on each). The reaction scheme for the synthesis of this product is provided in Figure 13. [00147] Example 19: Synthesis ofTridecaflouro-monomorpholino-di ropylamino)- phthalocyaninatozinc(II) [00148] A nucleophile mixture was prepared as follows: to 1-2 ml of propylamine were added 4 drops of each pyrrolidine and morpholine. This way there is an excess of the less reactive nucleophile (propylamine). In this mixture were dissolved 10 mg of F₁₆CoPc and then stirred at room temperature for 1 hour. An aliquot was taken and purified by silica gel chromatography using ethyl acetate as the eluent. A blue-green fraction was collected. The MALDI-MS shows the following substitution pattern:

[00149] The remaining reaction mixture was heated to 80°C for about 1 hour and then purified the same way. The collected fraction was green. The MALDI-MS shows the following substitution pattern:

[00150] The reaction scheme for the synthesis of this product is provided in Figure 14. [00151] Example 20: Synthesis ofDodecafluoro-monomorpholino-dipropylamino- monopyrrolidino-phthalocyaninatozinc(II) [00152] Another reaction was done using the same three nucleophiles as above, but this time in a consecutive way: first F₁₆CoPc (10 mg) was mixed with 1 ml of morpholine and stirred at room temperature for 10 minutes. Then 1 ml of pyrrolidine was added and the mixture was stirred for 15 more minutes. After this step the blue-green material was purified by silica gel chromatography using ethyl acetate as the eluent. After evaporating the solvent 1 ml of propylamine was added to the Pc and heated to 60-70°C for 1 hour. After that the propylamine was evaporated and the resulting green material submitted for MALDI-MS. The spectra shows the following substitution pattern:

[00153] The reaction scheme for the synthesis of this product is provided in Figure 15. [00154] Example 21: Synthesis ofTetraanilino-di(3,3-dimethylbutanoxy)-decafluoro- phthalocyaninatozinc(II) [00155] F₁₆ZnPc (10 mg) was dissolved in 1-2 ml of aniline and heated to 200°C for 3 hours. The mixture was purified by silica gel chromatography using THF and then (on a second column) ethyl acetate as the eluting solvents. An aliquot (grey-blue) was submitted for MALDI-MS. The spectra shows substitution of 4 to 7 fluorines by aniline. To the remaining product was added a mixture of 1 ml 3,3-dimethylbutanol and 0.1 ml nBuLi, which had been stirred at room temperature for 15 minutes before. The whole reaction mixture was then heated to 120°C for 26 hours. No colour change appeared. Purification was done by using ethyl acetate for silica gel chromatography. The MALDI-MS shows the following substitution pattern:

[00156] The reaction scheme for the synthesis of this product is provided in Figure 16. [00157] Example 22: Synthesis ofTeti'a(cyclohexylamino)-mono(3,3-dimethylbutanoxy)- undecafluoro-phthalocyaninatozinc(II) [00158] A mixture of 1 ml 3,3-dimethylbutanol and 0.1 ml nBuLi, which had been stirred at room temperature for 15 minutes before, was added to the product of the final step of example 14. The whole reaction mixture was then heated to 120°C for 6 hours. No colour change appeared. Purification was done by silica gel chromatography using ethyl acetate as the eluent. The MALDI-MS shows the following substitution pattern:

[00159] The reaction scheme for the synthesis of this product is provided in Figure 17. [00160] Example 23: Synthesis ofTri-(3,3-dimethylbutanoxy)-heptafluoro- hexapyrrolidino-phthalocyaninatozinc(II) [00161] F₁₆ZnPc (10 mg) was dissolved in 1-2 ml of pyrrolidine and heated to 50°C for 25 minutes. The mixture turned from blue to brownish olive green. After that pyrrolidine was evaporated and the remaining material was purified by silica gel chromatography using ethyl acetate as the eluting solvent. The MALDI-MS at this step shows substitution of 5 to 7 fluorines by pyrrolidine. This product was then added a mixture of 1 ml 3,3-dimethylbutanol and 0.1 ml nBuLi, which had been stirred at room temperature for 15 minutes before. The whole mixture was heated to 120°C for 6 hours and then purified the same way as the first step. A brown fraction was collected. The MALDI-MS shows the following substitution pattern:

[00162] The reaction scheme for the synthesis of this product is provided in Figure 18. [00163] Example 24: Synthesis ofPenta(cyclohexylamino)-mono(5-ethyl-l,3-dioxane-5- methyloxy)-decafluoro-phthalocyaninatozinc(II) [00164] Fι₆ZnPc (10 mg) was dissolved in 1-2 ml of cyclohexylamme and heated to 100°C for 1 hour. The product was purified by silica gel chromatography using ethyl acetate as the eluent, and then added to a mixture of 1 ml 5-ethyl-l,3-dioxane-5-methanol and 0.1 ml nBuLi, which had been stirred at room temperature for 15 minutes before. The whole reaction mixture was heated to 100-120°C for 1 hour. The product was purified by silica gel chromatography using a mixture of hexanes: ethyl acetate = 1:1 as the eluting solvent. A brown fraction was collected. The MALDI-MS shows the following substitution pattern:

[00165] The reaction scheme for the synthesis of this product is provided in Figure 19. [00166] Example 25: Synthesis ofPenta(cyclohexylamino)-mono(5-ethyl-l,3-dioxane-5- methyloxy)-decafluoro-phthalocyaninatozinc(II) [00167] Considering that the use of nBuLi with an alcohol in the second step might cause α-deprotonation on the aheady attached amine, the order of the steps was switched. Since the amines are weaker nucleophiles than the alkoxides care was taken to ensure that too many fluorines were not replaced in the first step so that the amine can react as well. So this time a mixture of 1 ml 5-ethyl-l,3-dioxane-5-methanol and 0.1 ml was stirred for 15 minutes at room temperature. After that 10 mg of F₁₆ZnPc were added and the whole mixture was heated to 80°C for 3 h. Since no colour change occurred the mixture was heated to 115°C for 10 more minutes. Purification was done by silica gel chromatography using THF as the eluent. Since it did not remove all the alcohol (sample still liquid after the column), the sample was dried by air flow over night (it did not work very well either). The MALDI-MS shows substitution of 0 to 3 fluorines by the alcohol. This product was then dissolved in cyclohexylamine and heated to 110°C for 1 hour. Purification was done by silica gel chromatography using ethyl acetate as the eluent. The MALDI-MS shows the following substitution pattern:

[00168] The reaction scheme for the synthesis of this product is provided in Figure 20. A mixture of 2-3 ml 1-octanethiol and 0.1 ml nBuLi was stirred at room temperature for 15 minutes, then added to the product of the previous step and heated to 120°C for 5 hours. The thiol was then evaporated by leaving the open flask under an air flow over night. The remaining product was purified by silica gel chromatography using ethyl acetate as the eluent. A brown fraction was collected. [00169] Example 26: Synthesis ofTetra(cyclohexylamine)-tetra(cyclohexylmethoxy)- octafluoro-phthalocyaninatozinc(II) [00170] A mixture of 2-3 ml cyclohexylmethanol and 0.1 ml nBuLi was stirred at room temperature for 15 minutes, then added to 10 mg F₁₆ZnPc and heated to 110-120°C for 1 hour. The colour changed from blue to blue-green. The product was purified by silica gel chromatography using ethyl acetate as the eluent. The MALDI-MS shows substitution of 0 to 10 fluorines by the alcohol. The sample was then dissolved in 1-2 ml of cyclohexylamine, heated to 100-130°C for 30 minutes (colour changed to dark olive green) and purified by silica gel chromatography using ethyl acetate as the eluent. The MALDI-MS shows the following substitution pattern:

[00171] The reaction scheme for the synthesis of this product is provided in Figure 21. [00172] Example 27: Synthesis ofTri(3,3-dimethylbutanoxy)-octafluoro-pentamorpholino- phthalocyaninatozinc(II) [00173] A mixture of 2-3 ml 3,3-dimethylbutanol and 0.1 ml nBuLi was stirred at room temperature for 15 minutes, then added to 10 mg of F₁₆ZnPc and heated to 115°C for 3 hours (colour remained blue). The product was purified by silica gel chromatography using ethyl acetate as the eluent. The MALDI-MS shows substitution of 0 to 8 fluorines by the alcohol. The sample was then dissolved in 1-2 ml of morpholine, heated to 90-110°C for 2-3 hours (colour changed to olive green) and purified the same way as the first step. The MALDI-MS shows the following substitution pattern:

[00174] The reaction scheme for the synthesis of this product is provided in Figure 22. [00175] Example 28: Synthesis ofTetra(cyclohexyloxy)-octafluoro-tetramorpholino- phthalocyaninatozinc(II) [00176] A mixture of 2-3 ml cyclohexanol and 0.1 ml nBuLi was stirred at room temperature for 15 minutes, then added to 10 mg of F₁₆ZnPc and heated to 100-110°C for 2 hours and to 120-130°C for 1 hour. The product was purified by silica gel chromatography using ethyl acetate as the eluent. The MALDI-MS shows substitution of 0 to 7 fluorines by the alcohol. The sample was then dissolved in 1-2 ml of morpholine, heated 100°C for 30 minutes (colour changed from blue to olive green) and purified the same way as the first step. The MALDI-MS shows the following substitution pattern:

[00177] The reaction scheme for the synthesis of this product is provided in Figure 23. [00178] Example 29: Synthesis ofTetra(cyclohexylmethyloxy)-di(cyclopentylamino)- mono(3,3-dimethylbutanoxy)-nonafluoro-phthalocyaninatozinc(II) [00179] A mixture of 2-3 ml 3,3-dimethylbutanol and 0.1 ml nBuLi was stirred at room temperature for 15 minutes, then added to 10 mg of F₁₆ZnPc and heated to 120°C for 40 minutes. The product was purified by silica gel chromatography using ethyl acetate as the eluent. The MALDI-MS shows substitution of 3 to 11 fluorines by 3,3-dimethylbutanol. A mixture of 2-3 ml cyclohexylmethanol and 0.1 ml nBuLi was stirred at room temperature for 15 minutes, then added to the product of the first step and heated to 120°C for 30 minutes. The product was purified by silica gel chromatography using ethyl acetate as the eluent. The MALDI-MS shows the following substitution pattern:

[00180] To the product of this second step was then added 2 ml cyclopentylamine and the mixture was heated to 100-110°C for 30 minutes. The colour turned from blue-green to blackish purple. The product was purified by silica gel chromatography with ethyl acetate as the eluent. The MALDI-MS shows the following substitution pattern:

[00181] The reaction scheme for this product is provided in Figure 24. [00182] Example 30: Synthesis cfDi(cyclohexylmethyloxy)-mono(cyclohexyloxy)- tetra(cyclopentylamino)-nonafluoro-phthalocyaninatozinc(II) [00183] A mixture of 2-3 ml cyclohexanol and 0.1 ml nBuLi was stirred at room temperature for 15 minutes, then added to 10 mg of F₁₆ZnPc and heated to 120°C for 30 minutes. The product was purified by silica gel chromatography using ethyl acetate as the eluent. The MALDI-MS shows substitution of 0 to 3 fluorines by cyclohexanol. A mixture of 2-3 ml cyclohexylmethanol and 0.1 ml nBuLi was stirred at room temperature for 15 minutes, then added to the product of the first step and heated to 120°C for 2 hours. The product was purified by silica gel chromatography using ethyl acetate as the eluent. The MALDI-MS shows the following substitution pattern:

[00184] To the product of this second step was then added 2 ml cyclopentylamine and the mixture was heated to 100-110°C for 30 minutes. The colour turned from blue to blackish purple. The product was purified by silica gel chromatography with ethyl acetate as the eluent. The MALDI-MS shows the following substitution pattern:

[00185] A mixture of 2-3 ml 1-octanethiol and 0.1 ml nBuLi was stirred at room temperature for 15 minutes, then added to the product of the third step and heated to 120°C for 5 hours. The thiol was then evaporated by leaving the open flask under an air flow over night. The remaining product (a brown liquid) was purified by silica gel chromatography using ethyl acetate as the eluent. The reaction scheme for this product is provided in Figure 25. [00186] Example 31: Synthesis ofOctafluoro-octa(l-octanyloxy)-phthalocyaninatozinc(II) [00187] A mixture of 1 -2 ml 1 -octanol and 0.1 ml nBuLi was stirred at room temperature for 15 minutes, then added to 10 mg of F₁₆ZnPc and heated to 120°C for 2 hours. The product was purified by silica gel chromatography using ethyl acetate as the eluent. The MALDI-MS shows substitution of 5 to 10 fluorines by 1-octanol. A mixture of 1-2 ml 1-octanethiol and 0.1 ml nBuLi was stirred at room temperature for 15 minutes, then added to the product of the first step and heated to 120°C for 5 hours. The colour turned from light blue-green to yellow-green. The thiol was then evaporated by leaving the open flask under an air flow over night. The remaining product (a viscous liquid) was purified by silica gel chromatography using ethyl acetate as the eluent. [00188] The reaction scheme for this product is provided in Figure 26. [00189] Example 32: Synthesis ofTetrafluoro-dodeca(cyclohexylmethyloxy)- phthalocyaninatozinc(II) [00190] 1-2 ml cyclohexylmethanol stirred at room temperature for 15 minutes and then added to 10 mg of F₁₆ZnPc. The mixture was heated to 120°C for 20 hours. The colour turned from blue to green. The product was purified by silica gel cliromatography using ethyl acetate as the eluent. The MALDI-MS shows substitution of 10 to 13 fluorines by the alcohol. [00191] The reaction scheme for this product is provided in Figure 27. [00192] Although the invention has been described with reference to certain specific embodiments, various modifications thereof will be apparent to those skilled in the art without departing from the spirit and scope of the invention as outlined in the claims appended hereto

TABLE 1: Spectroscopic Data for Example 1

TABLE 2: Spectroscopic Data for Example 2

TABLE 3: Spectroscopic Data for Example 3

TABLE 4: Spectroscopic Data for Example 4

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method for solubilizing a fluorinated phthalocyanine compound said method comprising the step of:

-providing a nucleophilic species having a nucleophilic site, wherein the nucleophilic site is selected from the group consisting of C, Si, N, P, O, or S atoms;

-reacting the nucleophilic species with the fluorinated phthalocyanine compound, the reaction of the nucleophilic species with the fluorinated phthalocyanine compound producing a soluble substituted phthalocyanine compound substituted at peripheral and non-peripheral sites, the substituted phthalocyanine compound having a general formula [N^sub _jMPcXk] wherein:

-Pc is a phthalocyanine general structure;

-M is a nonmetal, a metal, a metal oxide, or a metal halide

-N^su is a peripheral or non-peripheral substituent which has been covalently bonded to the phthalocyanine (Pc) by means of a nucleophilic substitution reaction;

-X is a halogen atom, which in one aspect is a fluorine atom; further, j and k are integers wherein j ranges between 1 and 16 and k ranges between 0 and 15 wherej+k=16.

2. The method of claim 1, wherein the nucleophile is activated prior to reaction with the fluorinated phthalocyanine compound.

3. The method of claim 1 wherein more than one nucleophile is used.