Stabilized and reactive fluorinated phthalocyanine-functionalized solid-state support composites

Abstract

A new class of organic-inorganic hybrid composite materials, composites of a fluoroalkyl fluorophthalocyanine and a solid-state support containing an imidazole group. The new class of composite materials can be used as a heterogeneous catalyst for the heterogeneous oxidation organic molecules in aqueous and some organic solvents systems is claimed.

Claims

1. An organic-inorganic hybrid composite including a phthalocyanine moiety coupled to at least one axial ligand, X, wherein the organic-inorganic hybrid composite is represented by Formula I: ##STR00005## wherein each R.sub.f is independently selected from the group consisting of a fluorine atom, a fluorocarbon group containing from 1 to 18 carbon atoms, a fluorine containing group, a non-fluorine containing group, and combinations thereof, wherein at least one R.sub.f includes a fluorine atom, wherein M is one or more of a metal atom or a non-metal atom, wherein X is represented by Formula II: ##STR00006## wherein n is from 1 to about 6 wherein Y is selected from the group consisting of an oxide, M.sub.xO.sub.y, a polymer, and an inert material.

2. The organic-inorganic hybrid composite material of claim 1, wherein an amount of X is about 90 to about 99.9 weight percent (wt %), based on the total weight of the organic-inorganic hybrid composite material.

3. The organic-inorganic hybrid composite material of claim 1, wherein the phthalocyanine moiety does not leach in a reaction medium.

4. The organic-inorganic hybrid composite material of claim 3, wherein the reaction medium comprises a solvent.

5. The organic-inorganic hybrid composite material of claim 1, wherein M is a metal in oxidation state of (II), (III), or (IV).

6. The organic-inorganic hybrid composite material of claim 1, wherein R.sub.f is the same or different and is one of perfluoroisopropyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, or isomers thereof or combinations thereof.

7. The organic-inorganic hybrid composite material of claim 1 where n is 3.

8. The organic-inorganic hybrid composite material of claim 1, wherein Y is silicon dioxide (SiO.sub.2).

9. The organic-inorganic hybrid composite material of claim 1, wherein Y is an oxide, and the oxide is M.sub.xO.sub.y, wherein x and y are small numbers selected such that the overall charge of M.sub.xO.sub.y is about zero.

10. The organic-inorganic hybrid composite material of claim 9, wherein M is selected from the group consisting of silicon (Si), titanium (Ti) and zironcium (Zr) and wherein x=1 and y=2.

11. The organic-inorganic hybrid composite material of claim 9, wherein M is Al and x=2 and y=3.

12. The organic-inorganic hybrid composite material of claim 1, wherein Y is selected from the group consisting of a polymer and an inert material.

13. A method for catalytic oxidation of a material selected from the group consisting of a mercaptan, an amino-substituted phenyl compound, and a substituted anthracene, comprising: mixing the composite of claim 1 and the material in a solvent to form a mixture; catalyzing the formation of a reactive intermediate species in the mixture; and oxidizing the material with the reactive intermediate species.

14. The method of claim 13, wherein the solvent includes water.

15. The method of claim 13, wherein catalyzing the formation of a reactive intermediate species further comprises: illuminating the mixture to catalyze the formation of the reactive intermediate species.

16. The organic-inorganic hybrid composite material of claim 1, wherein the inert material includes charcoal or graphite.

17. The organic-inorganic hybrid composite material of claim 9, wherein M is selected from the group consisting of silicon (Si), titanium (Ti), zirconium (Zr) and aluminum (Al).

18. The organic-inorganic hybrid composite material of claim 4, wherein the solvent is selected from the group consisting of dichloromethane, tetrahydrofuran (THF), ethyl acetate and acetone.

19. The organic-inorganic hybrid composite material of claim 4, where the solvent is a non-polar solvent.

20. The organic-inorganic hybrid composite material of claim 1, wherein M includes a metal or non-metal selected from the group consisting of Zn.sup.2+, Mg.sup.2+, low-spin Fe.sup.2+, Ru.sup.2+, Pt.sup.2+, Ti.sup.4+, Si.sup.4+, Co.sup.2+, Sn.sup.4+, Al.sup.3+, Ga.sup.3+, In.sup.3+, and mixtures thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1. Representation of fluoroalkyl metal fluorophthalocyanine type materials useful in combination with certain solid-state materials as a component in the present invention.

(2) FIG. 2. Schematic representation of hybrid composite material synthesis and structure metal-organic phthalocyanine materialimidazole-SiO.sub.2 solid-state support. The dotted line signifies a non-covalent interaction between the metal M and an N atom of the imidazole.

(3) FIG. 3. Graphics of O.sub.2 uptake in the aerobic oxidation of 4-fluoro benzene thiol.

(4) FIG. 4. Time dependent UV-Vis Spectrum of AVS in D.sub.2O in the presence of Si-Imi-F.sub.64PcZn illuminated with visible light.

(5) To aid in the understanding of the subject invention, the following examples are provided as illustrative thereof; however, they are merely examples and should not be construed as limitations on the claims.

DETAILED DESCRIPTION

(6) A functionalized fluorine containing phthalocyaninesolid state support composite of the present application can have the formula (R.sub.f).sub.16PcM-X. All isomers, e.g., structural isomers, stereoisomers, mirror-image enantiomers, etc. are possible in the above mentioned formula for a functionalized fluorine containing phthalocyaninesolid state support composite of the present application.

(7) In some embodiments, a functionalized fluorine containing phthalocyaninesolid state support composite may be represented by formula (I):

(8) ##STR00001##

(9) It should be noted that the formulation R.sub.f is equivalent to the formulation F.sub.nRPcML, but more descriptive. The sum of the F atoms, n represents the total numbers of F atoms present in the R.sub.f groups. The X ligands is equivalent to the L while the definition of the R.sub.f groups, see below, includes that of R.

(10) R.sub.f can be the same or different and can be selected from the group consisting of fluorine (F), a fluorocarbon containing from 1 to 18 carbon atoms, a fluorine containing group, a non-fluorine containing group, and combinations thereof. Exemplary non-fluorine containing groups may include hydrogen, nitro, amino, chloro, sulfonate, thiol, hydroxo, carboxylic, hydrocarbon, or groups that are known in the art to act as aromatic substituents. In one embodiment, a hydrocarbon group can be attached to the aromatic ring of the phthalocyanine, and another non-fluorine containing group can be attached to the hydrocarbon. In some embodiments, at least one R.sub.f contains a fluorine atom. The inclusion of fluorine in at least one R.sub.f can provide higher thermal and chemical stability.

(11) R.sub.f can include fluoroalkyl (e.g., perfluoroalkyl), fluoroalkylcylic, fluoroalkylbicyclic, fluoroaryl, fluoroheteroaryl, fluoroheterocyclic, and fluoroheterobicyclyl. It will be obvious to those skilled in the art that other fluorocarbons having 1 to 18 carbon atoms can be used.

(12) The alkyl group of the fluoroalkyl may be methyl, ethyl, propyl, butyl, cycloalkyl and functionalized alkyl groups. The functionalized alkyl group may be methylamino, dimethylamino, ethylamino, diethylamino, propylamino, butylamino, alkoxy, alkylsulhydryl, haloalkyl and phosphoryl groups. The alkoxy may be methoxy, levulinyl, carboxy, ethoxy, propoxy and functionalized alkoxy groups. The functionalized alkoxy group may be O(CH.sub.2)q-R, where q=2-4 and R is NH.sub.2, OCH.sub.3, or OCH.sub.2CH.sub.3. The alkoxyalkyl group may be methoxyethyl, and ethoxyethyl. The haloalkyl group may be CF.sub.3, CBr.sub.3, CCl.sub.3 and CI.sub.3.

(13) The aryl group of the fluoraryl may be phenyl, benzyl, phenol, naphthyl, bi-aryl, trityl, functionalized trityl carbobenzyloxy, functionalized carbobenzyloxy. The functionalized trityl group may be trityl-R, where R is OC(CH.sub.3).sub.3, OCH.sub.3, or OCH.sub.2CH.sub.3. The functionalized carboxybenzyloxy group may be selected from the group consisting of CO-aryl-R, where R is a halogen (Cl, F, Br, I, alkyl or alkoxyalky (OC(CH.sub.3).sub.3, OCH.sub.3, or OCH.sub.2CH.sub.3).

(14) The alkylcyclic group of the fluoroalkylcyclic may be cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

(15) The alkylbicyclic group of the fluoroalkylbicyclic may be di-cyclobutyl, di-cyclopentyl and di-cyclohexyl.

(16) The heterocyclic group of the fluoroheterocyclic may be pyrimidinyl, pyrrolo, pyridinyl, oxazolinyl, aza-oxazolinyl, thio-oxazolinyl, thiophenyl, furyl, or imidazolyl.

(17) The heterobicyclic group of the fluoroheterobicyclic may be purinyl, steroyl, indoyl and quinolyl.

(18) M can be a metal or non-metal. The metal is not limited to a diamagnetic metal. Exemplary metals can Zn.sup.2+, Mg.sup.2+, low-spin Fe.sup.2+, Ru.sup.2+, Pt.sup.2+, or Ti.sup.4+. Exemplary non-metals can include Si.sup.4+.

(19) M can be in complex with, or covalently bound to at least one axial ligand, X, which is the imidazole functionalized support. In some embodiments, M can be in complex with or covalently bound to up to two axial ligands. In one embodiment, X may be represented, in one embodiment, by Formula (II):

(20) ##STR00002##

(21) In Formula II, n can be from one to about 6. In the embodiments described herein n is 3.

(22) Y as represented in Formula (II) can be selected from the group consisting of an oxide, M.sub.xO.sub.y, where x and y are small numbers selected such that the overall charge is zero. M could be, for example, Si, Ti, Zr, for which x=1, y=2; Al for which x=2, y=3 etc. In addition, Y can be a polymer, an inert support (for example charcoal or graphite) etc. In one embodiment Formula II is Si-Imidazole.

(23) Each axial ligand can be any atom or group of atoms, similar or different that can coordinate M. Each axial ligand may be independently selected, and may include H, alkylamino, alkylthio, alkoxy, alkylseleno, alkylsulfonyl, C(S)NHC.sub.6H.sub.11O.sub.5, OC(O)CH.sub.3, OC(O), CS, CO, CSe, OH, O (oxo) and an alkyl group having from 1 to 12 carbon atoms, or (CH.sub.2).sub.nN((CH).sub.o(CH.sub.3)).sub.2, wherein n is an integer from 1 to 12; and o is an integer from 1 to 11.

(24) In some embodiments, M may be represented by (G).sub.aY[(OSi(CH.sub.3).sub.2(CH.sub.2).sub.bN.sub.c(R).sub.d(R).sub.e).sub.fX.sub.g].sub.p, wherein a is 0 or 1, b is an integer from 2 to 12, c is 0 or 1, d is an integer from 0 to 3, e is an integer from 0 to 2, f is 1 or 2, g is 0 or 1, and p is 1 or 2. Y may be selected from Si, Al, Ga, Ge, or Sn. R may be selected from H, CH.sub.3, C.sub.2H.sub.5, C.sub.4H.sub.9, C.sub.4H.sub.8NH, C.sub.4H.sub.8N, C.sub.4H.sub.8NCH.sub.3, C.sub.4H.sub.8S, C.sub.4H.sub.3O, C.sub.4H.sub.8Se, OC(O)CH.sub.3, OC(O), CS, CO, CSe, OH, C.sub.4H.sub.8N(CH.sub.2).sub.3CH.sub.3, (CH.sub.2).sub.2N(CH.sub.3).sub.2, an alkyl group having from 1 to 12 carbon atoms, and (CH.sub.2).sub.nN((CH.sub.2).sub.o(CH.sub.3)).sub.2, wherein n is an integer from 1 to 12; and o is an integer from 1 to 11. R may be selected from H, SO.sub.2CH.sub.3, (CH.sub.2).sub.2N(CH.sub.3).sub.2, (CH.sub.2).sub.11CH.sub.3, C(S)NHC.sub.6H.sub.11O.sub.5, an alkyl group having from 1 to 12 carbon atoms, and (CH.sub.2).sub.nN((CH.sub.2).sub.o(CH.sub.3)).sub.2, wherein n is an integer from 1 to 12; and o is an integer from 1 to 11. G may be selected from OH and CH.sub.3. X may be selected from I, F, Cl, or Br.

(25) M may include at least one metal, at least one non-metal, or a combination of a metal and a non-metal. Exemplary M include AlOSi(CH.sub.3).sub.2(CH.sub.2).sub.3N(CH.sub.3).sub.2, AlOSi(CH.sub.3).sub.2(CH.sub.2).sub.3N(CH.sub.3).sub.3.sup.+T, CH.sub.3SiOSi(CH.sub.3).sub.2(CH.sub.2).sub.3N(CH.sub.3).sub.2, HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.3N(CH.sub.3).sub.2, HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.3N(CH.sub.3).sub.3.sup.+T, Si[OSi(CH.sub.3).sub.2(CH.sub.2).sub.3N(CH.sub.3).sub.3.sup.+T].sub.2, Si[OSi(CH.sub.3).sub.2(CH.sub.2).sub.4NH.sub.2].sub.2, Si[OSi(CH.sub.3).sub.2(CH.sub.2).sub.4NHSO.sub.2CH.sub.3].sub.2, HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.4NHSO.sub.2CH.sub.3, HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.3N(CH.sub.2CH.sub.3)(CH.sub.2).sub.2N(CH.sub.3).sub.2, Si[OSi(CH.sub.3).sub.2(CH.sub.2).sub.4 NHCSNHC.sub.6H.sub.11O.sub.5].sub.2, Si[OSi(CH.sub.3).sub.2(CH.sub.2).sub.3N(CH.sub.3).sub.2].sub.2, HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.3OCOCH.sub.3, HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.3OH, Si[OSi(CH.sub.3).sub.2(CH.sub.2).sub.3N(CH.sub.2CH.sub.3)(CH.sub.2).sub.2N(CH.sub.3).sub.2].sub.2, HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.3NC.sub.4H.sub.8O, AlOSi(CH.sub.3).sub.2(CH.sub.2).sub.3N.sup.+(CH.sub.3).sub.2(CH.sub.2).sub.11CH.sub.3I.sup., HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.8N(CH.sub.3).sub.2, Si[OSi(CH.sub.3).sub.2(CH.sub.2).sub.3NC.sub.4H.sub.8O].sub.2, HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.3NC.sub.4H.sub.8S, HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.3N(CH.sub.2).sub.3(CH.sub.3).sub.2, HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.3NCS, HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.3N[(CH.sub.2).sub.3N(CH.sub.3).sub.2].sub.2, HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.3NC.sub.4H.sub.8NCH.sub.3, Si[OSi(CH.sub.3).sub.2(CH.sub.2).sub.3NC.sub.4H.sub.8NCH.sub.3].sub.2, HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.3NC.sub.4H.sub.8N(CH.sub.2).sub.3CH.sub.3, Si[OSi(CH.sub.3).sub.2(CH.sub.2).sub.3NC.sub.4H.sub.8NH].sub.2, or pharmaceutically acceptable salts thereof.

(26) M can include HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.3N(CH.sub.3).sub.2, HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.3N(CH.sub.2CH.sub.3)(CH.sub.2).sub.2N(CH.sub.3).sub.2, HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.3NC.sub.4H.sub.8O, HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.8N(CH.sub.3).sub.2, or pharmaceutically acceptable salts thereof. In one embodiment, M is HOSiOSi(CH.sub.3).sub.2(CH.sub.2).sub.3N(CH.sub.3).sub.2 or a pharmaceutically acceptable salt thereof. M can be two protons, e.g. H.sup.+.

(27) As stated above, the phthalocyanines could produce reactive oxygen species via electron transfer or via transferring accumulated solar energy into dioxygen. The activated oxygen species can react further with a variety of chemical and biological substrates.

(28) In one embodiment, the functionalized fluorine containing phthalocyaninesolid state support composite is suspended either in water or a suitable solvent therefore to create a slurry. The slurry is then combined with the substrate (e.g. the thiol in the example below) on which the phthalocyaninesolid state support composite is intended to operate. Exemplary substrates are described in U.S. Patent Application Publication Nos. 20150284592 and 20150315137. Such substrates are well known to one skilled in the art and not described in detail herein. Once the desired reaction has occurred, the phthalocyaninesolid state support composite is separated from the substrate using conventional separation techniques such as filtration, centrifugation, etc. Such separation techniques are well known to one skilled in the art and not described in detail herein.

(29) In some embodiments, a method for catalytic oxidation of a material can include mixing a inorganic-organic hybrid composite, such as Si-Imi-F.sub.64PcZn, and the material in a solvent to form a mixture. The mixture can be catalyzing to form of a reactive intermediate species in the mixture. The material can be oxidized by the reactive intermediate species. In some embodiments, the mixture can be illuminated to form the reactive intermediate species. In some embodiments, the material may be selected from the group consisting of a mercaptan, an amino-substituted phenyl compound, and a substituted anthracene. An exemplary mercaptan may be a thiol. An exemplary amino-substituted phenyl compound may be aniline. An exemplary substituted anthracene may be Anthracene-9, 10-bis(ethanesulphonate), sodium salt, dihydrate (AVS).

Example 1

(30) Preparation of F.sub.nRPcM complexes, FIG. 1. F.sub.64PcM complexes, n=64, RR.sub.fC.sub.3F.sub.7, M=Co, Zn to be used in subsequent examples, were produced using published procedures [See Bench. B., et al. Synthesis and structure of a biconcave cobalt perfluorophthalocyanine and its catalysis of novel oxidative carbon-phosphorus bonds formation by using air, Angewandte Chemie (2002) 41, 750; Bench, B., et al., Introduction of bulky perfluoroalkyl groups at the periphery of zinc perfluorophthalocyanine: chemical, structural, electronic, and preliminary photophysical and biological effects, Angewandte Chemie (2002) 41, 747, both of which are incorporated by reference herein. The NH.sub.2F.sub.51PcM complexes, n=51, RNH.sub.2, M=Co, Zn were prepared following a published procedure [See Patel, H. PhD Thesis. Seton Hall University, August 2015 which is incorporated by reference herein].

(31) Heterogeneous F.sub.nRPcML preparation, n=51, RNH.sub.2, M=Co. The target, NH.sub.2F.sub.51PcCo Si-Imidazole was prepared by dissolving 10.0 mg of NH.sub.2F.sub.51PcCo in 25 mL tetrahydrofuran (THF) and refluxing the mixture for 30 min. 1.0 g of imidazole functionalized silica (3 mmol of imidazole per gm of silica gel) was added and the reaction mixture was refluxed for another 30 min. The weight ratio phthalocyanine/silica gel was 1%, the molar ratio of imidazole/cobalt was 500:1. The functionalized silica gel turned green in color due to the loading of the catalyst and the solution became colorless. The green silica particles were collected by filtration, washed with THF/ethyl acetate and dried in oven at 150 C. for 24 h before use. Heterogeneous F.sub.nRPcML preparation, n=64, RR.sub.f, M=Co. The target, F.sub.64PcCo Si-Imidazole was prepared using the same procedure as that used for NH.sub.2F.sub.51PcCo Si-Imidazole and maintaining the same, 500:1 molar ratio of imidazole/cobalt.

Example 2

(32) The compositions described herein having SiO.sub.2Imidazole supports for fluorinated phthalocyanines are an improvement over fluorinated phthalocyanines with SiO.sub.2 supports. In order to illustrate the differences, phthalocyanine leaching experiments were carried out. Firstly, the NH.sub.2F.sub.51PcCo SiO.sub.2 and F.sub.64PcCo SiO.sub.2 composites were prepared by evaporating a suspension of SiO.sub.2 in THF solutions of phthalocyanines and drying the solids in an oven at 150 C. for 24 h.

(33) The NH.sub.2F.sub.51PcCo SiO.sub.2 and F.sub.64PcCo SiO.sub.2 solids prepared as described above were suspended in a series of organic solvents including THF, dichloromethane, ethyl acetate, acetone, ethanol, methanol, etc. After stirring for a few minutes the suspensions were filtered and the liquids examined by UV-Vis spectroscopy. The spectra exhibited the trace known for the phthalocyanines used to prepare the solids. In addition, the solids lost their blue-green color and became white. Taken together, the results indicate that the phthalocyanine SiO.sub.2 hybrids are unstable in organic solvents regardless of the presence of the functional H.sub.2N group. In contrast, when the same experiment was run using NH.sub.2F.sub.51PcCo Si-Imidazole and F.sub.64PcCo Si-Imidazole no leaching was observed, but only when weakly polar or non-polar solvents were used. Examples of other weakly polar solvents include hydrocarbon solvents, a halogenated hydrocarbon solvents, esters, ethers, amides, ketones, etc. Examples of such solvents include dichloromethane, THF, ethyl acetate and acetone. Leaching was observed in more highly polar solvents such as methanol and ethanol.

Example 3

(34) The catalytic oxidation of thiols (mercaptans) was used to demonstrate the catalytic activity of the present composites. The catalysis is related to the MEROX (MERcaptans OXidations) process, widely utilized in the petroleum industry to convert corrosive and foul smelling thiols into disulfide products. The reaction obeys an overall stoichiometry of 4:1, RSH/O2, according to equation 1.
4RSH+O.sub.2.fwdarw.2RSSR+2H.sub.2O(1)
Mechanistically, equations 2-4 outline the solution oxidations. PcCo stands for a phthalocyanine cobalt catalyst. R is a hydrocarbon.
2RSH+2HO.sup..fwdarw.2RS.sup.+2H.sub.2O(2)

(35) ##STR00003##
H.sub.2O.sub.2+2RSH.fwdarw.RSSR+2H.sub.2O(4)

(36) The process includes very reactive intermediate species: peroxide, O.sub.2.sup.2, RS.sup..circle-solid. radicals and superoxide, O.sub.2.sup..circle-solid.. These species may attack the catalyst.

(37) Reaction mixtures for thiols oxidations consisted of 50 mL 101 M PcCo in THF and, in case of hybrid catalysts 100.0 mg of NH.sub.2F.sub.51PcCo Si-Imidazole in 50 mL of THF (1:100 w/w catalyst:silica imidazole ratio), 1 mL NaOH 0.25% (aq) and 7.1 mmol of the thiol of choice, 755 L 4-fluorobenzene thiol. Volumes under 1 mL were measured with a calibrated micro pipette. The thiol:NaOH:catalyst molar ratio was 13000:120:1. Oxygen consumption, FIG. 3, was measured with an automatic gas titrator. FIG. 3a shows O.sub.2 consumption in the catalyzed auto-oxidation of 4-fluorobenzene thiol in THF. FIG. 3b presents the initial reaction rates, shown as linear fits on the first data points recorded within the first 17 min of each reaction. Table 1 is listing the relevant catalytic parameters.

(38) TABLE-US-00001 TABLE 1 Parameters of the catalyzed auto-oxidation of 4-fluorobenzene thiol under O.sub.2 Rate.sup.a TOF.sup.b TON.sup.c TON.sub.max [mol [mol [mol [mol O.sub.2 RSH s.sup.1 RSH RSH TON Catalyst min.sup.1] mol Pc.sup.1] mol Pc.sup.1] mol Pc.sup.1] TON.sub.max No catalyst 14.97 6365* 7100* 0.90 NH.sub.2F.sub.51PcCo 31.17 4.16 12890 14200 0.91 NH.sub.2F.sub.51PcCoSi- 43.44 5.08 11225 12456 0.90 Imidazole .sup.aInitial reaction rate, mol O.sub.2 min.sup.1, calculated from the linear fit portion of the graphs of FIG. 3. .sup.bTurnover frequency (TOF), mol substrate s.sup.1 mol PC.sup.1, calculated under pseudo-first order conditions. .sup.cTotal oxidation number (TON) after 6 h, calculated stoichiometrically as: (final recorded O.sub.2 volume [mL]/molar volume of O.sub.2 at 25 C. [24.45 mL mmol.sup.1) (4000 [mol substrate mmol O.sub.2.sup.1/nPc [mol Pc]). *For the non-catalyzed auto-oxidation, turnover number is calculated as: TON = (final recorded O.sub.2 volume [mL]/molar volume of O.sub.2 at 25 C. [24.45 mL mmol.sup.1) 4000 [mol substrate mmol O.sub.2.sup.1]; TON.sub.max = n.sub.RSH = 7100 [mol substrate].

(39) The data establish that the solid-state hybrid, NH.sub.2F.sub.51PcCo Si-Imidazole is catalytically active with rate, surprisingly, higher than that of the homogeneous catalyst, NH.sub.2F.sub.51PcCo. Moreover, as its can be noted from FIG. 3, the support, Si-Imidazole acts actually as an inhibitor, the reaction rate being substantially lower compared with the rate observed in the absence of the support or catalyst. Thus, it is clear that the hybrid, NH.sub.2F.sub.51PcCo Si-Imidazole exhibits unprecedented synergistic interactions that are beneficial for technological applications. Considering the bonding detailed in Table 1, between the Pc material and the solid-state support, the composite phthalocyanine-solid state support defines a qualitatively new chemical material, i.e. a hybrid that exhibits some properties, including chemical reactive strengths, not found in either of the two components.

Example 4

(40) The production of singlet oxygen was monitored by photolysis of a singlet oxygen trap, Anthracene-9, 10-bis(ethanesulphonate), sodium salt, dehydrate (AVS) to form an endoperoxide product (AVO.sub.2) as shown in Scheme 1 below. AVS was selected to detect singlet oxygen production by heterogeneous photo sensitizer Si-Imi-F.sub.64PcZn. .sup.IH NMR and UV-Vis spectroscopy were used to detect AVSO.sub.2.

(41) ##STR00004##

(42) 10.85 mg of AVS was dissolved in 25.0 mL of D.sub.2O to form a mixture. 100.0 mg of Si-Imi-F.sub.64PcZn was added to the mixture. The mixture was illuminated with a 300 W halogen projector lamp for 3 h under an oxygen balloon at 25 C. The light was filtered with a 0.01M potassium chromate solution to allow only visible light to reach the mixture. The progress of the reaction was monitored by UV-Vis spectroscopy as shown in FIG. 4.

(43) Control experiments that monitored AVS in the absence of Si-Imi-F.sub.64PcZn or in the presence of only silica imidazole with aF.sub.64PcZn catalyst demonstrated stability in the UV-Vis spectrum and 1HNMR indicated the presence of AVS (not shown). However, Example 4 showed a decrease in the intensity of the 398 nm absorption over a period of 3 hours. This decrease is consistent with the trapping of singlet oxygen by AVS to form AVSO.sub.2. Moreover, a preliminary kinetics analysis (not shown) of the reaction reveals 1.sup.st orders kinetics, which is consistent with the expected changes upon trapping of singlet oxygen. Further catalyst performance was confirmed by .sup.IH NMR (not shown) which was characteristic of the AVSO.sub.2, which confirms production of singlet oxygen by Si-Imi-F.sub.64PcZn.

(44) It will be understood by those skilled in the art that, although the subject invention has been described above in relation to embodiments thereof variations and modifications can be effected in these preferred embodiments without departing from the scope and spirit of the invention.