WO2012103309A2 - Systèmes polymères contenant des motifs chromophores pour photocatalyse et dissociation d'eau - Google Patents

Systèmes polymères contenant des motifs chromophores pour photocatalyse et dissociation d'eau Download PDF

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WO2012103309A2
WO2012103309A2 PCT/US2012/022686 US2012022686W WO2012103309A2 WO 2012103309 A2 WO2012103309 A2 WO 2012103309A2 US 2012022686 W US2012022686 W US 2012022686W WO 2012103309 A2 WO2012103309 A2 WO 2012103309A2
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polymer
reaction
chem
transition metal
photocatalyst
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PCT/US2012/022686
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English (en)
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WO2012103309A3 (fr
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Wenbin Lin
Zhigang Xie
Cheng Wang
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The University Of North Carolina At Chapel Hill
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Publication of WO2012103309A3 publication Critical patent/WO2012103309A3/fr

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Definitions

  • a first aspect of the invention is a polymer (e.g., a photocatalytic polymer) that contains chromophoric units therein (e.g., covalently coupled therein, in the polymer backbones and/or side chains).
  • the polymer comprises: (a) a first ligand as a first repeating monomelic unit therein (e.g., as part of the polymer backbones and/or side chains); (b) a transition metal (e.g., Ru, Ir, Fe, Co, etc.) complexed with said first ligand to form a chromophoric unit or transition metal photocatalyst therewith; and (c) optionally but preferably at least one additional ligand (e.g., one or two) complexed with said transition metal to form said chromophoric unit or transition metal photocatalyst; and (d) optionally but preferably a second monomelic unit copolymerized with said first monomelic unit.
  • the first monomelic unit comprises a compound of the formula A'BCD', wherein A' and D' are (depending upon the particular polymerization reaction employed) covalent bonds or independently selected linking groups (e.g., a ethenyl, ethynyl, halo, carboxyl, amide, etc.), and B and C are independently selected coordinating groups (e.g., heteroalkyl, heteroaryl) conjugated to said transition metal.
  • A' and D' are (depending upon the particular polymerization reaction employed) covalent bonds or independently selected linking groups (e.g., a ethenyl, ethynyl, halo, carboxyl, amide, etc.)
  • B and C are independently selected coordinating groups (e.g., heteroalkyl, heteroaryl) conjugated to said transition metal.
  • a further aspect of the invention is a polymer as described herein for use as a photocatalyst.
  • a further aspect of the invention is a method of making a polymer, particularly a photocatalytic polymer, comprising: reacting a first monomer with a second monomer; wherein: said first monomer comprises a compound of the formula ABCD, wherein A and D are independently selected reactive groups (e.g., ethenyl, ethynyl, halo, amino, carboxy), and B and C are independently selected coordinating groups (e.g., heteroalkyl, heteroaryl); and said second monomer comprises a compound the formula X(YZ) n , wherein X is an organic or silyl group (e.g., carbon, Si, phenyl, te/ -butyl), Y is an organic group (preferably aryl, particularly phenyl), Z is a reactive group (e.g., ethenyl, ethynyl, halo, amino, carboxy), and n is 3 or 4.
  • a and D are independently selected reactive
  • a further aspect of the present invention is a polymer produced by a process as described herein.
  • a further aspect of the invention is a method of carrying out a photocatalytic reaction by contacting one or more substrates to a photocatalyst and exposing said photocatalyst to light to produce one or more products.
  • the method is characterized by the improvement comprising employing a polymer or catalyst system of any preceding claim as said photocatalyst.
  • FIG. 1 Characterization of Ir-PCP and Ru-PCP: a) SEM and b) TEM images of the Ir-PCP. The scale bars represent 200 nm. c) TGA, d) FT-IR, e) Nitrogen adsorption isotherms at 77K, and f) uncorrected emission spectra.
  • the Ir-PCP emission spectrum (red line) was taken when excited at 380 nm. The broad emission at around 458.5 nm comes from fluorescence of the framework.
  • the Ru-PCP emission spectrum blue line was taken when excited at 450 nm. The broad emission at around 522.5 nm comes from fluorescence of the framework.
  • FIG. 1 Pore size distribution of Ir-PCP and Ru-PCP calculated by density functional theory (DFT).
  • Figure 11 provides a thermogravimetric analysis (TGA) of Ru-COF.
  • Figure 12 provides an emission spectra (excitation wavelength is 450nm.
  • Figure 13 provides SEM (scanning electron micrograph) photographs.
  • Figure 14 provides an FT-IR spectra.
  • Figure 15 provides a BET plot.
  • Figure 18 TEM images of 1 (a) and 2 (b) on a carbon-coated Cu/Ni grid.
  • Figure 21 Time-resolved phosphorescence decays of 1 and 2 and monomers Ru-1 a nd Ru-2 (excitation: 440 nm; emission: 660 nm).
  • Light refers to ambient or directed light as well as light from natural or artificial sources. Light of any suitable wavelength may be used, with light in the visible spectra in some embodiments preferred.
  • Reactive group may be any suitable reactive group, depending upon the particular coupling or polymerization reaction used. Examples include, but are not limited to, carboxy, carboxylic acid including activated carboxylic acid, hydroxy, epoxy, halo, amino, substituted amino, epoxy, isocyanate, sulfonyl, and sulfonate groups; triflate, boronic acid, B(OH) 2 , tin or organotin, zinc or zinc halide, and aldehyde, MgBr, - (trialkoxysilyl)propylamine, omega-(trialkoxysilyl)alkyl bromomethylacetamide, thiol, etc. See, e.g., US Patent Nos. 4,293,476; 4,555,546; and 7,173,102.
  • solvent herein may be any suitable aqueous or organic solvent (including mixtures thereof), including but not limited to (a) non-polar solvents such as pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, etc., (b) polar aprotic solvents such as dichloromethane, tetrahydrofuran, ethyl acetate, acetone, dimethylformaniide, acetonitrile, dimethyl sulfoxide, etc., and (c) polar protic solvents such as formic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol, acetic acid, water, etc., and combinations of all of the foregoing.
  • non-polar solvents such as pentane, cyclopentane, hexane,
  • Aqueous solvents can be neutral, basic, or acidic aqueous solvents.
  • Transition metal as used herein includes, but is not limited to, Ru, Ir, Fe, Co, Cu, Ti, Pt, Ir, Rh, Ag, Ni, etc.
  • the first monomer comprises a compound of the formula ABCD, wherein A and D are independently selected reactive groups (e.g., ethenyl, ethynyl, halo, amino, carboxy), and B and C are independently selected coordinating groups (e.g., heteroalkyl, heteroaryl).
  • a and D are independently selected reactive groups (e.g., ethenyl, ethynyl, halo, amino, carboxy)
  • B and C are independently selected coordinating groups (e.g., heteroalkyl, heteroaryl).
  • said first monomer is a ligand complexed with a transition metal (e.g., Ru, Ir, Fe, or Co) to form a transition metal photocatalyst therewith, and with at least one (e.g., one or two) additional ligand optionally complexed with said transition metal to form said transition metal photocatalyst.
  • a transition metal e.g., Ru, Ir, Fe, or Co
  • the second monomer comprises a compound the formula X(YZ) bond, .
  • X is an organic or silyl group (e.g., carbon, Si, phenyl, ferf-butyl)
  • Y is an organic group (preferably aryl, particularly phenyl)
  • Z is a reactive group (e.g., ethenyl, ethynyl, halo, amino, carboxy), and n is 3 or 4.
  • Any suitable ligand system can be used in the monomers.
  • Particular examples are bipyridine or phenylpyridine, but other ligand systems such as porphyrin systems can also be used.
  • Non-limiting examples of suitable monomers for carrying out the present invention include:
  • suitable monomers for carrying out the present invention include any of the foregoing illustrated structures, where (a) the specific reactive groups shown (NH 2 , C0 2 H, ethynyl, bromo, and B(OH) 2 ) are replaced by any of the other reactive groups noted hereinabove; (b) the specific aryl groups shown are replaced by different aryl groups (e.g., one or two additional hetero atoms such as oxygen, nitrogen or sulfur are substituted in the ring, and/or a carbon or hetero atom is deleted to form a corresponding five member ring, etc.), (c) a "spacer" group such a C1-C2 alkylene is inserted between rings systems (e.g., between two phenyls, two pyridines, or a phenyl oand a pyridine), or between a ring system and a reactive group, (d) any of the aforesaid rings shown are optionally substituted (e.g.
  • polymerization of monomers can be carried out by any suitable polymerization or coupling reaction.
  • suitable polymerization or coupling reaction examples include, but are not limited to: Negishi coupling reaction, a Heck coupling reaction, a Suzuki coupling reaction, a Hiyama coupling reaction, a Sonogashira coupling reaction, a Stille coupling reaction, a Kumada coupling reaction, a Buchwald-Hartwig amination reaction, an allyl substitution reaction, an enolate arylation reaction, a hydroformylation reaction, a carbonylation reaction, a hydrosilylation reaction or a boronylation reaction. See, e.g., US Patent No. 7250510.
  • Additional more particular examples include, but are not limited to, Suzuki-Miyaura, Murahashi, Kumada- Corriu, Kumada-Tamao, Nozaki, Nozaki-Oshima, Negishi, Tamao-Kumada, Hiyama- Hatanaka, Migita-Kosugi, Buchwald-Hartwig, Murahashi, Cyanation, dehydrohalogenation, . alpha. -"Carbonyl" Arylation, Cadiot-Chodkiewicz, catalytic ether formation, catalytic . alpha. -arylations of ketones, dehalogenation, and catalytic thioether formation reactions, etc. See, e.g., US Patent No. 7,442,800.
  • the present invention provides a polymer (e.g., a photocatalytic polymer) that contains clu'omophoric units therein (e.g., covalently coupled therein, in the polymer backbones and/or side chains).
  • a polymer e.g., a photocatalytic polymer
  • clu'omophoric units therein e.g., covalently coupled therein, in the polymer backbones and/or side chains.
  • the polymer comprises: (a) a first ligand as a first repeating monomelic unit therein (e.g., as part of the polymer backbones and/or side chains); (b) a transition metal (e.g., Ru, Ir, Fe, Co, etc.) complexed with said first ligand to form a chromophoric unit or transition metal photocatalyst therewith; and (c) optionally but preferably at least one additional ligand (e.g., one or two) complexed with said transition metal to form said chromophoric unit or transition metal photocatalyst; and (d) optionally but preferably a second monomeric unit copolymerized with said first monomelic unit.
  • a transition metal e.g., Ru, Ir, Fe, Co, etc.
  • the first monomeric unit comprises a compound of the formula A'BCD', wherein A' and D' are (depending upon the particular polymerization reaction employed) covalent bonds or independently selected linking groups (e.g., a ethenyl, ethynyl, halo, carboxyl, amide, etc.), and B and C are independently selected coordinating groups (e.g., heteroalkyl, heteroaryl) conjugated to said transition metal.
  • A' and D' are (depending upon the particular polymerization reaction employed) covalent bonds or independently selected linking groups (e.g., a ethenyl, ethynyl, halo, carboxyl, amide, etc.)
  • B and C are independently selected coordinating groups (e.g., heteroalkyl, heteroaryl) conjugated to said transition metal.
  • the second monomeric unit comprises a compound of the formula X(Y-) n , wherein X is an organic or silyl group (e.g., carbon, Si, phenyl, fer/-butyl), Y is an organic group (preferably aryl, particularly phenyl), and n is 3 or 4.
  • X is an organic or silyl group (e.g., carbon, Si, phenyl, fer/-butyl)
  • Y is an organic group (preferably aryl, particularly phenyl)
  • n is 3 or 4.
  • the polymer is a porous crosslinked polymer.
  • Porous crosslinked polymers including crystalline covalent-organic frameworks, can be built from well-designed organic precursors and represent a new class of robust, nanoporous materials. 5 Like their porous metal-organic framework (MOF) counterparts, 6 PCPs have shown great promise in gas storage and separation and light harvesting. 7 Just like recently developed catalytic MOFs, 8 PCPs can serve as an ideal platform for incorporating molecular catalytic modules into highly stable, recyclable, and reusable heterogeneous catalyst systems by taking advantage of their permanent porosity and the ability to tune their compositions and properties at the molecular level.
  • MOF metal-organic framework
  • PCPs are advantageous over MOFs as photocatalysts since many MOFs are constructed from metal connecting points with unfilled d orbitals which can readily quench the photoexcited states of the photocatalytic building units.
  • Other polymeric systems containing chromophoric units in the polymer backbones and/or side chains can also be used for the photocatalytic reactions.
  • the polymer is thermally stable at 300 or 350 °C in air at atmospheric pressure for one or two hours.
  • the polymer has (a) an average poor diameter between 1 or 2 and 45 or 50 Angstroms; and/or (b) an average cumulative pore volume (cmVg) of from 0.01 or 0.1 to 0.9 or 1.
  • the polymer has a weight average molecular weight of at least 100, 500, 1 ,000, or 5,000 daltons.
  • the polymer has a weight average molecular weight of not more than 10,000, 50,000, 100,000, or 500,000 daltons.
  • Particular non-limiting examples of polymers of the invention include, but are not limited to:
  • octacarbonyldicobalt (Co 2 (CO) 8 )-catalyzed alkyne trimerization reaction products such as:
  • the polymers of the present invention are combined with a solvent in which the polymer is insoluble to provide a heterogeneous catalyst system.
  • a catalyst system can comprise (a) 0.1 or 1 percent to 80 or 90 percent by weight of a polymer as described herein (generally, in solid insoluble form, such as a particulate form), in combination with (b) from 10 or 20 to 99 or 99.9 percent by weight of a solvent ⁇ e.g., in the form of a liquid, gas, or supercritical fluid) (note in some embodiments, the solvent itself may also be a reactant).
  • a further aspect of the invention is a method of carrying out a photocatalytic reaction by contacting one or more substrates to a photocatalyst and exposing said photocatalyst to light to produce one or more products.
  • the method is characterized by the improvement comprising employing a polymer or catalyst system of any preceding claim as said photocatalyst.
  • Such methods may be carried out in accordance with known techniques, utilizing the catalysts and systems described herein, or variations thereof that will be apparent to those skilled in the art.
  • reactions examples include, but are not limited to: water splitting, reduction of carbon dioxide to form methanol, methane, or carbon monoxide; enone cycloaddition reaction, an enentioselective alpha-trifluoromethylation of an aldehyde reaction, an enantioselective alpha-benzylation of an aldehyde reaction, a dehalogenation reaction, an aza-henry reaction, a radical addition to an indole reaction, a C-H functionalization of a heterocycle with a malonate, an alpha oxymination, an oxyamination of an enamine and andehyde, an oxidative coupling of an amine, an oxidation of an alcohol, and hydrogen evolution.
  • the catalyst is advantageously recycled.
  • the method thus further comprises the steps of: separating said polymer from the product of said reaction (e.g., by first separating the polymer from the solvent), and then recycling said polymer in a subsequent reaction (e.g., by recombining said polymer with either fresh solvent, or the same solvent from which said product has been removed).
  • reactions that can be catalyzed by the catalysts and catalyst systems of the present invention include, but are not limited to, the following:
  • PCPs are active in catalyzing visible light-driven Aza-Henry reactions between nitromethane or nitroethane and tertiary aromatic amines, a-arylation of bromomalonate via intermolecular C-H functionalization, and oxyamination of an aldehyde with 2,2,6,6- tetramethylpiperidinyl- 1 -oxy (TEMPO).
  • TEMPO 2,2,6,6- tetramethylpiperidinyl- 1 -oxy
  • Co-polymerization of the monomer [(ppy) 2 Ir(debpy)]Cl or [(bpy) 2 Ru(debpy)]Cl 2 with tetra(4- ethynylphenyl)methane was achieved through Co 2 (CO)8-mediated trimerization of the end alkyne groups of the monomers in dioxane or dichloroethane at 1 15 °C for 10 min (Scheme 1).
  • the resulting brown solids were stirred in concentrated hydrochloric acid at r.t. for 2 h to remove all the Co species, and then washed with various solvents to afford Ir-PCP and Ru- PCP in 97 % yields.
  • the Ir- and Ru-PCPs were characterized by thermogravimetric analysis (TGA), inductively coupled plasma-mass spectrometry (ICP-MS), infrared spectroscopy (IR), nitrogen adsorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and powder X-ray diffraction PXRD).
  • TGA thermogravimetric analysis
  • ICP-MS inductively coupled plasma-mass spectrometry
  • IR infrared spectroscopy
  • SEM scanning electron microscopy
  • TEM transmission electron microscopy
  • PXRD powder X-ray diffraction
  • the Ir-PCP and Ru-PCP are insoluble in water, concentrated acids, and all of the organic solvents tested.
  • the PCPs are stable in air up to 350 °C as revealed by TGA (Figure lc).
  • the Ir and Ru catalyst loadings for Ir-PCP and Ru-PCP were determined by ICP-MS to be 4.5 wt % and 2.2 wt %, respectively.
  • the absence of the carbon-hydrogen stretching peak of the C ⁇ C-H group around 3300 cm "1 in the IR spectra of the Ir-PCP and Ru-PCP suggested that most of the alkyne groups in the starting materials have been consumed to form benzene rings in the PCPs, consistent with a high degree of polymerization (Figure Id).
  • Ir-M and Ru-M are Ir monomer [(ppy) 2 Ir(debpy)]Cl and Ru monomer [(bpy) 2 Ru(debpy)]C3 ⁇ 4, respectively; c with nitromethane as solvent; d with nitroethane as solvent.
  • PCPs also catalyzed Aza-Henry reactions between nitroethane and tertiary aromatic amines (Table 1 , Entry 5-8). Interestingly, most of the PCP-catalyzed Aza-Henry reactions have higher conversions than those catalyzed by their homogeneous counterparts.
  • Ru-PCP catalyzed a-arylation of bromomalonate and oxyamination of 3- phenylpropanal.
  • the Ru-PCP catalyst was readily recovered and re-used for these reactions.
  • Ir and Ru phosphors have been successfully integrated into porous crosslinked polymers via cobalt catalyzed alkyne trimerization.
  • the resultant framework materials are stable in various solvents, including concentrated hydrochloric acid, and are thermally and oxidatively stable in air up to 350 °C.
  • These phosphorescent Ir- and Ru-based PCPs were shown to be highly active, recyclable and reusable heterogeneous photocatalysts in Aza-Henry reactions of a variety of amine substrates. This work highlights the potential of using PCPs as a stable and molecularly tunable platform for developing highly efficient heterogeneous photocatalysts for a number of important organic transformations.
  • Powder X-ray diffraction (PXRD) analyses were carried out on a Bruker SMART APEX II Diffractometer using Cu radiation, processed with the APEX II package using PILOT plug- in.
  • a Varian 820-MS Inductively Coupled Plasma-Mass Spectrometer (ICP-MS) was used to determine Ir content.
  • Scanning electron microscopy (SEM) and transmission electron microscope (TEM, JEM lOOCX- II ) were used to image the particles, using a Hitachi 4700 Field Emission Scanning Electron Microscope.
  • a Cressington 108 Auto Sputter Coater equipped with a Au/Pd (80/20) target and an MTM-10 thickness monitor was used to coat the samples with a conductive layer before taking SEM images.
  • Each SEM sample was prepared by first suspending the material in ethanol, then a drop of the suspension was placed on a glass slide and the solvent was allowed to evaporate.
  • Thermogravimetric analysis (TGA) was performed using a Shimadzu TGA-50 equipped with a platinum pan, and all samples were heated at a rate of 5 °C per minute under air. Nitrogen adsorption experiments were performed with a Quantachrome Autosorb-lC. Quenching experiments were performed using a Shimadzu RF-5301 PC Spectrofluorophotometer.
  • bipyridine were synthesized by following the published procedures. ' [Ir(ppy) 2 Cl ] 2 (200 mg, 0.19 mmol) and 5,5'-diethyneyl-2,2'-bipyridine (76 mg, 0.37 mmol) were suspended in 15 mL 1 : 1 MeCN/CHCl 3 under argon. After refluxing overnight, evaporation of the solvent under reduced pressure yielded a red solid, which was dissolved in a small amount of CHC1 3 and then filtered through a short silica column. A reddish-orange band was eluted by 1 : 1 MeCN/0,4N KN0 3 .
  • the reaction flask was then put in an oil bath that was preheated at 115 °C.
  • the brown solution started to solidify after about 5 min, The reaction mixture was continued with heating for another 5 min, and then the flask was lifted above. the oil bath to cool to room temperature.
  • the brown solid was collected by filtration and washed with methanol and water.
  • the solid was redispersed in concentrated HCl for 2 h.
  • the product was obtained by filtration, and washed with water and methanol and dried under vacuum. Yield: 113 mg (97%).
  • the Ru-PCP was prepared similarly in quantitative yields.
  • Figure 2 shows the p Powder X-ray diffraction (PXRD) of Ir-PCP and Ru-PCP. The low intensity broad peaks indicate the amorphous nature of the PCPs.
  • Figure S2 shows the pore size distribution of Ir-PCP and Ru-PCP calculated by density functional theory (DFT).
  • Figure S3 shows the cumulative pore volume of Ir-PCP and Ru-PCP calculated by DFT.
  • Figure S4 shows an idealized structure of the Ir-PCP.
  • Ru-PCP 1 mg was suspended in 3 mL of CH 3 N0 2 and ground by vigorously stirring overnight to yield small and uniform particles.
  • the substrate la was added stepwise to the degassed suspension, and phosphorescence spectra were collected under steady stirring after the addition of la every time.
  • Figure 6 shows a Stern-Volmer plot of Ru-PCP quenching by la, compared to that of the homogeneous monomer [(bpy)2Ru(debpy)]C12.
  • Stern-volmer constant for Ru-PCP is 23 NT 1 , and 20 M "1 for [(bpy) 2 Ru(debpy)]Cl 2 .
  • the mixture was cooled to room temperature, and the insoluble precipitated product was filtered and washed with acetonitrile, water, methanol, and acetone to remove any unreacted monomers or catalyst residues. Further purification of the product was carried out by stirring in methanol for 2 days and filtered it. The product was dried under vacuum for 24 H at 50 °C to give brown powder.
  • Gartner F. Sundararaju B., Surkus A. E., Boddien A., Loges B., Junge H., Dixneuf P. H., Beller M. Angew. Chem. Int. Ed. 2009, 48, 1 -5
  • 4,4'-bis[tri(isopropyl)silylethynyl]-2,2'-bipyridine was prepared by a Pd-catalyzed Sonogashira reaction between 4,4'-dibromo-2,2'-bipy 46 and [tri(isopropyl)silyl] acetylene in 93% yield.
  • Oxidative Eglinton coupling reactions of the two regioisomeric tetra(ethynyl) derivatives of Ru(bpy) 3 2+ were carried out with the CVLCI/ ⁇ , ⁇ , ⁇ ', ⁇ '- tetramethylethylenediamine catalyst under an oxygen atmosphere in acetonitrile at 35 °C for 0.5 h. 50
  • the resulting solids were washed with pyridine, methanol, water, and dried in vacuo to afford CPs 1 and 2 in 95% and 91% yield, respectively.
  • Both 1 and 2 are black-red amorphous powders that are insoluble in common organic solvents such as DMF, H 2 0, CH 3 CN, and resistant toward acids and bases.
  • ICP-MS inductively coupled plasma mass spectroscopy
  • FT- IR Fourier transform-infrared spectroscopy
  • TGA thermo gravimetric analysis
  • TEM transmission electron microscopy
  • Figure 17 shows the n Nitrogen sorption isotherms of 1 and 2 in at 77 .
  • IR spectra The degree of polymerization is indicated by the IR spectra.
  • IR spectra of monomers Ru-1 and Ru-2 showed a diagnostic absorption of carbon-hydrogen stretching peak of the C ⁇ C-H group at about 3180 cm “1 and 3200 cm “1 , respectively ( Figure 16). These peaks are mostly absent in the IR spectra of the CPs, indicating that most of the terminal alkyne groups in the monomers have been consumed in the oxidative Eglinton coupling reactions.
  • the particles are stable up to 200 °C in air, as revealed by TGA, which is consistent with previously reported CPs polymers based on butadiyne linkages. 51
  • Figure 18 shows the TEM images of 1 (a) and 2 (b) on a carbon-coated Cu/Ni grid.
  • the porosity of the CPs was investigated by nitrogen sorption measurements at 77 K. 1 exhibits a BET surface area of 198 m 2 /g whereas 2 shows a negligible BET surface area of 15 rn /g. These surface areas are significantly lower than the CPs based on tetrakis(4- ethynyl-phenyl)methane. 51"52 We attributed the low porosity of 1 and 2 to the bulky groups of the [Ru(bpy) 3 ] 2+ complexes in the polymer networks, which is known to reduce the porosity of CPs.
  • the TEM sample was prepared by first dispersing the CPs in methanol, and then placing them on carbon-coated Cu/Ni grids. TEM images of both 1 and 2 showed that they are aggregates of spherical nanoparticles of ⁇ 100 nm in diameter.
  • Figure 19 shows the steady-state absorption spectra of stirred suspensions of 1 and 2 in CH 3 CN (0.74 mg/50 mL) and dilute solutions of Ru-1 and Ru-2 in CH 3 CN (2x l0 "5 M). Absorption spectra of Ru-1 and Ru-2 are on a reduced scale (x 0.2).
  • Figure 20 shows the steady-state phosphorescence spectra of stirred suspensions of 1 and 2 in CH 3 CN (0.74 mg/50 mL) and dilute solutions of Ru-1 and Ru-2 in CH 3 CN (2x l0 "5 M).
  • CPs built from [Ru(bpy) 3 ] 2+ complexes act as insoluble but dispersible photosensitizers by taking advantage of redox-active MLCT excited states of the chromophores.
  • Steady-state UV-vis absorption and emission spectra and time-resolved phosphorescence spectra were recorded with a stirred suspension of 1 or 2 in CH 3 CN and dilute solutions of Ru-1 and Ru-2 monomers in CH 3 CN (2x l 0 "5 M). They all showed a broad absorption between 300-800 nm with two or three additional discernible absorption bands.
  • the absorption peak at -294 nm is assigned to the ⁇ * bipy ligands in the [Ru(bpy) 3 ] 2+ whereas the peak at -493 nm is attributed to the metal-to-ligand charge transfer ('MLCT) transition.
  • 'MLCT metal-to-ligand charge transfer
  • the phosphorescence maximum ⁇ ⁇ 3 ⁇ of 1 exhibited obviously red shift in comparison with monomer Ru-1 owing to the increased effective conjugation length of ligands in CP-1 and aggregation of 1 in the particle.
  • the phosphorescence lifetimes of the CPs were measured using an Edingburgh FLS 920 in the time-correlated photon counting mode. When excited at ⁇ 440 nm, the decays of monomers Ru-1 and Ru-2 and CP-1 were well fitted with a mono-exponential model, leading to emission lifetimes of 962 ns, 574 ns, and 423 ns, respectively.
  • the emission decay of 2 was fitted with a double-exponential model to give an averaged lifetime of 112 ns, indicating a much shorter-lived 3 MLCT phosphorescence.
  • the broad absorption bands together with relatively long excited state lifetimes of the CPs make them good candidates as heterogeneous photocatalysts.
  • Figure 21 shows the time-resolved phosphorescence decays of 1 and 2 and monomers Ru-1 a nd Ru-2 (excitation: 440 nm; emission: 660 nm).
  • Benzyl bromoacetate was chosen as the substrate and a 26 W fluorescent lamp was used as the light source. Benzyl bromoacetate was completely converted to benzyl acetate with 1 mol% loadings of photocatalyst 1 or 2 based on J H NMR spectra (data not shown). These results have been corroborated with high isolated yields of the benzyl acetate (92% for 1 and 86% for 2). A control reaction in the absence of the CPs gave ⁇ 10% conversion. The CP photocatalyst could also be recovered and reused without significant decrease in conversions and yields.
  • Ru chromophores in the interior of the polymers can effectively serve as light harvesting antemia to collect photon energy and transfer them to the reactive sites.
  • the Ru chromophores on the surface can either be directly excited by light or accept excited state energy from the interior of the polymer particle, 56 and then go through redox reactions to initiate the catalytic cycle.
  • Such a light- harvesting phenomenon was recently umambiguously demonstrated by Lin et al. in [Ru(bpy) 3 ] 2+ -derived MOFs. 57
  • the excellent photocatalytic activities are attributed to high content of light-absorbing Ru(bpy) 3 2+ chromophores as well as excited state energy migration from the chromophores in the interior of the polymer particle to the reactive sites on the surface of the polymer particle.
  • Thermo gravimetric analysis was performed using a Shimadzu TGA-50 equipped with a platinum pan, and all samples were heated at a rate of 5 °C per minute under air. Nitrogen adsorption experiments were performed with a Quantachrome Autosorb-lC 77K after activating under vacuum at 60 °C for 10 h. UV-vis spectra were recorded on a Perkin Elmer Lambda 35 UV-vis spectrometer. Steady-state and time-resolved emission spectra were recorded on an Edinburgh FLS 920.
  • Ru ⁇ 4,4'-bis[tri(isopropyl)silylethynyl]-2,2'-bipy ⁇ 2 (2,2 , -bipy)Cl2 (TIPS-Ru-1).
  • 2,2'- bipyridine (17.2 mg, 0.1 1 mmol) and bis ⁇ 4,4'-bis[(triisopropyl)silylethynyl]-2,2'- bipy ⁇ ruthenium dichloride 47 120 mg, 0.1 mmol
  • Ru[4,4 , -bis(ethynyl)-2,2 , -bipy] 2 (2,2'-bipy)Cl 2 (Ru-1).
  • Ru ⁇ 4,4'- bis[tri(isopropyl)silylethynyl]-2,2'-bipy ⁇ 2 (2,2'-bipy)Cl 2 160 mg, 0.12 mmol
  • TBAF 0.5 mmol, 0.5 mL
  • Ru ⁇ 5,5 -bis[(tri(isopropyl)silylethynyl]-2,2'-bipy ⁇ 2 (2,2 , «bipy)Cl 2 (TIPS-Ru-2): 2,2'-bipyridine (55.0 mg, 0.3 mmol) and bis ⁇ 5,5'-bis[tri(isopiOpyl)silylethynyl]-2,2'- bipy ⁇ ruthenium dichloride (360 mg, 0.1 mmol) were dissolved in a mixture of chloroform (20 mL) and EtOH (20 niL) and refluxed for 3 days.
  • Ru[5,S'-bis(ethynyl)-2,2 , -bipy] 2 (2,2 , -bipy)Cl 2 (Ru-2).
  • Ru ⁇ 5,5'- bis[tri(isopi pyl)silylethynyl]-2,2'-bipy ⁇ 2 (2,2'-bipy)Cl 2 160 mg, 0.12 mmol
  • TBAF 0.5 mmol, 0.5 mL
  • Ru-1 or Ru-2 (70 mg, 0.095 mmol) was added to a stirred mixture of CuCl (1 mg, 0.01 mmol) and N,iV;N',iV'-tetramethylethylenediamine (1 mL) in CH 3 CN (40 mL). 0 2 was bubbled through the mixture which was kept at 35 °C for 0.5 h. The solid was collected by filtration and washed with pyridine, methanol, water, and dried in vacuum. Further purification of the product was carried out by Soxhlet extraction with methanol for 24 h to afford the CP-1 (63 mg, 95%) or -2 (60 mg, 91%) as red-black powder, respectively.
  • Aerobic oxidative coupling of amines To a flame-dried 25 mL flask were added catalyst (O.Olequiv), benzylamine (38 ⁇ , 1.0 eq) (or other benzylamine derivatives), and the acetonitrile (10 mL). The reaction mixture was stirred at 60 °C at a distance of -10 cm from a 450 W Xe lamp. The conversion was obtained by integration of the NMR peaks.

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Abstract

Cette invention concerne un polymère (par ex., polymère photocatalytique) qui contient des motifs chromophores (par ex., couplés par covalence, dans le squelette et/ou les chaînes latérales du polymère). Dans certains modes de réalisation, le polymère comprend : (a) un premier ligand à titre de premier motif monomère répétitif (par ex., faisant partie du squelette et/ou des chaînes latérales du polymère) ; (b) un métal de transition (par ex., Ru, Ir, Fe, Co, etc.) formant un complexe avec ledit premier ligand pour constituer un motif chromophore ou un photocatalyseur de type métal de transition avec celui-ci ; et (c) éventuellement, mais de préférence, au moins un ligand supplémentaire (par ex., un ou deux) formant un complexe avec ledit métal de transition pour constituer ledit motif chromophore ou photocatalyseur de type métal de transition ; et (d) éventuellement, mais de préférence, un second motif monomère copolymérisé avec ledit premier motif monomère. Des compositions le contenant et des procédés pour l'utiliser sont également décrits.
PCT/US2012/022686 2011-01-26 2012-01-26 Systèmes polymères contenant des motifs chromophores pour photocatalyse et dissociation d'eau WO2012103309A2 (fr)

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