CN117510552A - Preparation of Fac-Ir (C≡N) 3 Method for photooxidation reduction of catalyst - Google Patents
Preparation of Fac-Ir (C≡N) 3 Method for photooxidation reduction of catalyst Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- 238000007539 photo-oxidation reaction Methods 0.000 title claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000012994 photoredox catalyst Substances 0.000 claims abstract description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 15
- KZLHPYLCKHJIMM-UHFFFAOYSA-K iridium(3+);triacetate Chemical compound [Ir+3].CC([O-])=O.CC([O-])=O.CC([O-])=O KZLHPYLCKHJIMM-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004729 solvothermal method Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 230000035484 reaction time Effects 0.000 claims abstract description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- SSABEFIRGJISFH-UHFFFAOYSA-N 2-(2,4-difluorophenyl)pyridine Chemical compound FC1=CC(F)=CC=C1C1=CC=CC=N1 SSABEFIRGJISFH-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- WWMRJCUZPJJWBC-UHFFFAOYSA-N 4-methyl-2-phenylpyridine Chemical compound CC1=CC=NC(C=2C=CC=CC=2)=C1 WWMRJCUZPJJWBC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 21
- 230000015572 biosynthetic process Effects 0.000 abstract description 20
- 239000002994 raw material Substances 0.000 abstract description 13
- 238000001308 synthesis method Methods 0.000 abstract description 8
- 238000006552 photochemical reaction Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 229910052741 iridium Inorganic materials 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006757 chemical reactions by type Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 238000005695 dehalogenation reaction Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- KJNZQKYSNAQLEO-UHFFFAOYSA-N 2-(4-methylphenyl)pyridine Chemical compound C1=CC(C)=CC=C1C1=CC=CC=N1 KJNZQKYSNAQLEO-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical group CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000000628 photoluminescence spectroscopy Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
- C07F15/004—Iridium compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing Fac-Ir (C≡N) 3 A method for preparing photo-redox catalyst, involve homogeneous catalyst, photo-redox catalyst field of photochemical reaction, this method uses trinuclear oxygen bridge iridium acetate complex and cyclometalated ligand (C≡N) as raw materials, regard triethylene glycol as solvent, heat for 8 hours at 290 deg.C through solvothermal method in the hydrothermal reaction kettle, get Fac-Ir (C≡N) by one-step high-efficient synthesis 3 The photooxidation reduction catalyst is washed by deionized water, methanol, acetone and the like for the second time to obtain the product with the purity of more than 99 percent, and the yieldGreater than 95%, and greater than 80 grams in bulk. The method uses the raw material trinuclear oxygen bridge iridium acetate complex which is cheap and easy to obtain and commercialized, the synthesis method which is obtained by using the trinuclear oxygen bridge iridium acetate complex as the raw material has high yield, the involved reaction steps are few, the purification method is simple, the reaction time is short, the purity of the obtained product is high, and the method is suitable for Fac-Ir (C≡N) with low cost 3 The batch preparation of the type photo-redox catalyst.
Description
Technical Field
The invention relates to the field of homogeneous catalysts and photo-redox catalysts for photochemical reactions, in particular to a method for preparing Fac-Ir (C≡N) 3 A method for preparing a Fac-Ir (C≡N) 3 type photo-redox catalyst by a solvothermal method realizes the Fac-Ir (C≡N) by the solvothermal method 3 And (3) one-step high-efficiency synthesis of the photo-redox catalyst.
Background
Along with the proposal of the concept of green chemistry and sustainable development, the innovation of traditional industrial chemistry with high energy consumption and heavy pollution is urgent, and organic photochemical synthesis like photosynthesis in nature is constantly pursued by chemists. The photochemical synthesis adopts light instead of heat, the reaction can be triggered by using visible light, ultraviolet light and an LED lamp, the reaction is usually carried out at a temperature lower than 100 ℃ even under normal temperature, and the photochemical synthesis can shorten complex synthesis steps, decomposition reactions or the generation of byproducts to the minimum or no generation at all, thereby improving the yield while ensuring the purity. Compared with the traditional chemical reaction, the photochemical reaction has the advantages of high efficiency, cleanness, safety, energy saving, various reaction types, mild reaction conditions, controllable selectivity and the like, is successfully applied to various reactions such as oxidation reaction, reduction reaction, dehalogenation reaction, tertiary amine oxidation reaction, cross coupling reaction, cycloaddition reaction, asymmetric catalytic reaction and the like, provides a new way for a plurality of challenging classical reactions, can realize the new application of the 'old reaction' under the condition of green temperature, is an important branch in the chemical synthesis field, and is one of the most active and vigorous leading edge technologies.
In photochemical reactions, photo-redox catalysts are the most central and critical. Fac-Ir (ppy) formed with phenylpyridine and derivatives as cyclometallated ligands 3 The photo-redox catalyst becomes the most extensive and commonly used photo-induced catalyst, has been successfully applied to various reactions such as oxidation reaction, reduction reaction, dehalogenation reaction, tertiary amine oxidation reaction, cross coupling reaction, cycloaddition reaction and asymmetric catalytic reaction, and is applied to more reaction types, becomes a research hotspot and development trend in the current photochemical synthesis field, and is widely applied to the fields such as pharmaceutical chemistry, agrochemical chemistry, material chemistry and the like.
Ir(C^N) 3 The type photo-redox catalyst is a homoleptic neutral molecule formed by coordination of 3 identical cyclometallated ligands (C≡N) and iridium (III), and has two isomers of the formula (fac-) and the formula (mer-) which are difficult to separate if formed in the reaction, resulting in fac-Ir (C≡N) 3 The synthesis of photo-redox catalysts is extremely difficult, ir (C≡N) reported in the literature 3 The synthesis route of the photooxidation reduction catalyst mainly comprises the following 6 types:
all the synthetic methods are to take hydrated iridium trichloride as a raw material, firstly prepare corresponding iridium chloride bridge dimer complex, and purify the product by adopting column chromatography separation. The first synthesis method is that under alkaline condition, glycerin is used as solvent, and the target compound is obtained through heating reflux reaction, the yield is about 75%, the product is accompanied with the generation of a warp-type structure, the synthesis and separation are difficult, and the purity is low; the second synthesis method is that after chloride ions in iridium chloride bridge dimer are removed through silver triflate, the silver triflate reacts with cyclometalated ligand, the solvent is glycol monoethyl ether, the reaction temperature is 90-100 ℃, the target compound is finally obtained, the yield can reach 85%, but expensive silver salt is used in the synthesis process, and the generated silver chloride is difficult to separate from the product; the third synthesis method is to heat and reflux the iridium acetylacetonate and the cyclometalated ligand in a glycerol solvent to obtain the target compound in one step, the purity of the product synthesized by the method is high, but the yield is only 70%, and the price of the iridium acetylacetonate serving as a raw material is extremely high; a fourth synthesis method is to use Ir (C≡N) 2 The (O≡O) -iridium phosphorescent complex reacts with cyclometallated ligand in glycerol solvent, and the method can also obtain high-purity products with the yield of about 85%, but Ir (C≡N) is used 2 The raw materials of the (O≡O) iridium phosphorescent complex are extremely expensive, and the cost of the photooxidation reduction catalyst is seriously increased; a fifth synthesis method is by Na [ Ir (acac) 2 Cl 2 ]And ring metal complexThe reaction of the reaction product with heating and refluxing in glycerin solvent gives the target compound in 40% yield and Na [ Ir (acac) 2 Cl 2 ]Raw materials are also not readily available, and the sixth synthesis is by Ir (acac-O, O) 2 (acac-C 3 )(H 2 O) and a cyclometallated ligand are heated and subjected to reflux reaction in a glycerol solvent to obtain a target compound, wherein the yield of the method can reach 85 percent, but Ir (acac-O, O) 2 (acac-C 3 )(H 2 O) is also a raw material that is not readily available. Among these synthetic methods, other methods except the second method are all reacted at high temperature, and other methods except the 1 st and 2 nd synthetic methods all use raw materials which are not easily available, raising fac-Ir (C≡N) 3 The synthesis cost of the type photo-redox catalyst. The product obtained by the method 1 has a warp structure, is difficult to separate, and has low purity. The second method, through removing chloride ion by silver triflate, can realize the synthesis of the surface structure at a lower temperature (90-100 ℃), is the current synthesis of Ir (C≡N) 3 The most common method for iridium-based phosphorescent complexes, but this method uses a large amount of expensive silver salt, and the separation of the generated silver chloride and the product is extremely difficult during the mass synthesis, and the method is not suitable for mass production.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a novel method which is low in cost and high in efficiency and is suitable for batch preparation, the method takes a trinuclear oxygen bridge iridium acetate complex which is cheap and easy to obtain and commercialized as a raw material, and takes triethylene glycol with high boiling point as a solvent, and fac-Ir (C≡N) is efficiently prepared by one-step reaction with a cyclometalated ligand in a hydrothermal reaction kettle through a solvothermal method 3 The method can obtain high-purity fac-Ir (C≡N) by washing with simple secondary deionized water-methanol-acetone in turn 3 Photo-redox catalysts have been used in commercial fac-Ir (C≡N) 3 In the preparation of a batch of the type photo-redox catalyst.
The aim of the invention is mainly realized by the following technical scheme:
triethylene glycol is used as a solvent,the trinuclear oxygen bridge iridium acetate complex and a cyclometalated ligand C (mol ratio is 1:15) are used as raw materials, heated and reacted for a certain time at a certain temperature by a solvothermal method in a hydrothermal reaction kettle, cooled and filtered, and washed sequentially by water, methanol and acetone to obtain high-purity Fac-Ir (C (N)) 3 The photo-oxidation-reduction catalyst has a reaction yield of more than 95%, a purity of more than 99% and a batch of more than 80 g. The synthetic route is shown in FIG. 1.
The trinuclear oxygen bridge iridium acetate complex has a chemical structural formula:
further, the reaction step is one-step solvothermal synthesis.
Furthermore, the reaction vessel is a hydrothermal reaction kettle, the heating mode is solvothermal, certain vapor pressure can be generated in the reaction, and the reaction system has certain pressure.
Further, the heating temperature is 290 ℃.
Further, the reaction time was 8h.
Further, the C≡N ligand is 2-phenylpyridine, p-methylphenyl pyridine and 2, 4-difluorophenyl pyridine.
Further, the purification mode is that water, methanol and acetone are washed in sequence.
Through nuclear magnetic resonance hydrogen spectrum 1 H NMR) characterizes fac- (C≡N) 3 Structure of the type photo-redox catalyst.
Fac- (C≡N) was determined by High Performance Liquid Chromatography (HPLC) 3 Purity of the type photo-redox catalyst.
Fac- (C≡N) was studied by photoluminescence spectroscopy 3 Photophysical properties of the type photo-redox catalyst.
Compared with the prior art, the invention has the following beneficial effects:
the method takes a trinuclear oxygen bridge iridium acetate complex and a cyclometalated ligand which are cheap and easy to obtain and commercialized as raw materials, triethylene glycol as a solvent,heating in a hydrothermal reaction kettle at 290 ℃ for 8 hours by solvothermal, and obtaining fac- (C≡N) by one-step high-efficiency synthesis 3 The photo-redox catalyst is washed by simple secondary deionized water, methanol and acetone in turn to obtain the fac- (C≡N) with high purity 3 A type photo-redox catalyst. The invention adopts solvothermal heating, adopts glycol with high boiling point, and generates certain pressure under solvent steam, thereby avoiding mer-Ir (C≡N) 3 By-product production, the fac-Ir (C≡N) is realized 3 The high-efficiency synthesis and purification of the photo-oxidation-reduction catalyst has the yield of more than 95 percent, the purity of more than 99 percent and the batch quantity of more than 80 grams. The fac-Ir (ppy) is obtained by synthesis under conventional conditions (e.g., comparative example 1) 3 Compared with photo-redox catalyst, the method for synthesizing fac-Ir (C≡N) by solvothermal method 3 The type photo-redox catalyst has obvious advantages and technical progress in the aspects of synthesis yield and purity. Therefore, the synthesis method of the invention has high yield, few involved reaction steps, no need of column purification, simple purification method, high purity of the obtained product, easy amplification in batch, and suitability for Fac-Ir (C≡N) with low cost 3 The batch preparation of the photo-redox catalyst is beneficial to providing key raw materials for the related fields such as photochemical reaction and the like and promoting the rapid development of related industries.
Drawings
Fig. 1: the synthetic roadmap of the invention.
Fig. 2: ir (ppy) preparation according to the invention 3 Hydrogen spectrum of (a).
Fig. 3: ir (mppy) preparation according to the invention 3 Hydrogen spectrum of (a).
Fig. 4: ir (dfppy) preparation according to the invention 3 Hydrogen spectrum of (a).
Fig. 5: ir (ppy) preparation according to the invention 3 HPLC diagram of (2)
Fig. 6: ir (mppy) preparation according to the invention 3 HPLC diagram of (2).
Fig. 7: ir (dfppy) preparation according to the invention 3 HPLC diagram of (2).
Fig. 8: comparative example 1 preparation of Ir (ppy) 3 HPLC diagram of (2)
Fig. 9: the invention prepares Fac- (C≡N) 3 Photoluminescence spectra of photooxidation reduction catalysts。
Detailed Description
Example 1: fac-Ir (ppy) 3 Is synthesized by (a)
Referring to FIG. 1, a trinuclear oxygen bridge iridium acetate complex (54.1 g,44.93 mmol), 2-phenylpyridine (104.6 g,673.95 mmol) and 1200mL of triethylene glycol were sequentially added to a 2L hydrothermal reaction vessel, a lid sealed and covered with a glass reaction vessel was added, the hydrothermal reaction vessel was placed in an oven, heated at 290℃for 8 hours, the reaction system was cooled to room temperature, the hydrothermal reaction vessel was opened, filtered, and washed with water, methanol and acetone in this order to obtain fac-Ir (ppy) 3 84.55g of yellow solid product was obtained in 95.8% yield and 99.62% purity. 1 H NMR(400MHz,CDCl 3 ,δppm)：7.87(1H)，7.56(3H)，6.85(4H)。
Example 2: fac-Ir (mppy) 3 Is synthesized by (a)
Referring to FIG. 1, a trinuclear oxygen bridge iridium acetate complex (54.1 g,44.93 mmol), 2- (p-tolyl) pyridine (114.05 g,673.95 mmol) and 1200mL of triethylene glycol were sequentially added to a 2L hydrothermal reaction vessel, a lid sealed with the glass reaction vessel was added, the hydrothermal reaction vessel was placed in an oven, heated at 290℃for 8 hours, the reaction system was cooled to room temperature, the hydrothermal reaction vessel was opened, filtered, and washed with water, methanol and acetone in this order to obtain fac-Ir (mppy) 3 91.22g of yellow solid product was obtained in 96.7% yield and 99.39% purity. 1 H NMR(400MHz,DMSO,δppm)：8.04(2H)，7.72(2H)，7.62(2H)，7.03(2H)，6.60(2H)，6.50(2H)，5.74(1H)，1.99(6H)。
Example 3: fac-Ir (dfppy) 3 Is synthesized by (a)
Referring to FIG. 1, trinuclear oxygen bridge iridium acetate complex (54.10 g,44.93 mmol), 2, 4-difluorophenylpyridine (128.85 g,673.95 mmol) and 1200mL triethylene glycol were sequentially added to a 2L hydrothermal reaction vessel, a lid sealed to cover the glass reaction vessel was added, the hydrothermal reaction vessel was placed in an oven and heated at 290℃for 8 hours, the reaction system was cooled to room temperature, the hydrothermal reaction vessel was opened, filtered, and washed with water, methanol and acetone in this order to obtain fac-Ir (dffppy) 3 The yellow solid product was 98.69g in 96.0% yield and 99.60% purity. 1 H NMR(400MHz,DMSO,δppm)：8.21(3H)，7.87(5H)，7.25(1H)，7.12(3H)，6.67(1H)，6.14(2H)，5.78(1H)。
Comparative example 1: fac-Ir (ppy) 3 Is synthesized by (a)
Trinuclear oxygen bridge iridium acetate complex (5.41 g,4.49 mmol), 2-phenylpyridine (10.46 g,67.40 mmol) and 120mL of triethylene glycol were sequentially added into a 500mL three-necked round bottom flask, argon was filled for 3 times, the mixture was heated at 290℃for reflux reaction for 8 hours, cooled, filtered, washed with water, methanol and acetone in sequence, and fac-Ir (ppy) was obtained by column chromatography 3 The yellow solid product was 3.75g, yield 42.5% and purity 98.78%. 1 H NMR(400MHz,CDCl 3 ,δppm)：7.87(1H)，7.56(3H)，6.85(4H)。
In summary, embodiments of the present invention provide a method for preparing Fac-Ir (C≡N) in a batch manner 3 A one-step rapid and efficient synthesis method of a photo-redox catalyst.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions, such as changing the cyclometallated ligand and solvent, which are easily understood by those skilled in the art within the scope of the present invention are included in the scope of the present invention.
Claims (9)
1. Preparation of Fac-Ir (C≡N) 3 A method of forming a photooxidation reduction catalyst, the method comprising:
adding trinuclear oxygen bridge iridium acetate complex and cyclometalated ligand C≡N into a hydrothermal reaction kettle, adding a solvent, heating and reacting for a certain time at a certain temperature by a solvothermal method, cooling and filtering, and washing sequentially by water, methanol and acetone to obtain high-purity Fac-Ir (C≡N) 3 A type photo-redox catalyst.
2. The preparation of Fac-Ir (C≡N) according to claim 1 3 The method for preparing the photooxidation reduction catalyst is characterized in that the trinuclear oxygen bridge iridium acetate complex has the chemical structural formula:
3. the preparation of Fac-Ir (C≡N) according to claim 1 3 The method of the photooxidation reduction catalyst is characterized in that the molar ratio of the trinuclear oxygen bridge iridium acetate complex to the cyclometalated ligand C≡N is 1:15.
4. The preparation of Fac-Ir (C≡N) according to claim 1 3 A method for preparing a photo-redox catalyst, characterized by heating for a reaction time of 8 hours or more.
5. The preparation of Fac-Ir (C≡N) according to claim 1 3 A process for the type photo-redox catalyst characterized in that said cyclometallated ligand C N comprises any of 2-phenylpyridine, p-methylphenyl pyridine or 2, 4-difluorophenyl pyridine.
6. The preparation of Fac-Ir (C≡N) according to claim 1 3 The method of the type photo-redox catalyst is characterized in that the solvent is a high boiling point solvent.
7. The preparation of Fac-Ir (C≡N) according to claim 1 3 The method for preparing the photooxidation reduction catalyst is characterized in that the reaction temperature is 290 ℃, and the pressure generated by solvent vapor pressure is present in a reaction system.
8. Preparation of Fac-Ir (C≡N) according to any one of claims 1-6 3 The method of the photooxidation reduction catalyst is characterized in that the product is purified by adopting secondary deionized water, methanol and acetone to wash in sequence.
9. The preparation of Fac-Ir (C≡N) according to claim 6 3 A method of forming a photo-redox catalyst, characterized in that the solvent is triethylene glycol.
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