CN113372392A - Bis-isoindole iridium (III) complex and preparation method thereof - Google Patents
Bis-isoindole iridium (III) complex and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a bis-isoindole iridium (III) complex which is characterized in that the structural general formula of the bis-isoindole iridium (III) complex is shown as a formula I, wherein R is1、R2、R3Each independently selected from: H. one of an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group having 3 to 12 carbon atoms; ar (Ar)1And Ar2Each independently selected from aromatic ring containing groups. The diisoindolyl iridium (III) complex has structural diversity and high molar absorption coefficient, the maximum absorption wavelength can reach a near infrared region, and the diindolyl iridium (III) complex serving as a photosensitizer, an imaging reagent, a strong near infrared absorber and the like has good application prospects in the fields of biomedicine, material science and the like.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a bis-isoindole iridium (III) complex and a preparation method thereof.
Background
The metal iridium (III) complex has the advantages of high stability, relatively high phosphorescence quantum yield, relatively long emission life, adjustable spectrum and the like, and has potential application prospects in the fields of organic electroluminescence, biomedical imaging, sensing, catalysis and the like. Different main ligands and auxiliary ligands play an important role in the iridium (III) complex, and the iridium (III) and the complex act together to show different electron transition properties.
However, in the prior art, the main ligand of the iridium (III) complex is mostly a bipyridine system and its derivatives, and the preparation thereof generally involves metal catalytic preparation, and has the disadvantages of expensive raw materials, harsh reaction conditions, relatively difficult synthesis, and the like. In addition, the absorption wavelength of the bipyridyl system with electron deficiency is relatively short, the varieties of iridium complexes developed on the basis of the bipyridyl system are limited, and meanwhile, the absorption wavelength is relatively short and generally less than 550nm, so that the application and further development of the iridium complexes are limited.
On the basis, isoindolinone and pyrrole or derivatives thereof are condensed under phosphorus oxychloride and then dimerized to form a strong electron-rich bisisoindole ligand to replace an electron-deficient bipyridine system, and then the strong electron-rich bisisoindole ligand is coordinated with iridium (III) to prepare the novel bisisoindole iridium (III) complex. The raw materials used in the preparation method are commercialized, the raw materials are easy to obtain, the steps are simple, and the reaction is efficient. The near-infrared bis-isoindoline iridium (III) complex has structural diversity, can be realized by substituent group change, has adjustable spectrum and relatively large molar absorption coefficient (up to 25500 cm)-1) The maximum absorption wavelength can reach 710nm in the near infrared region, and the tail absorption can reach 900 nm. The absorption wavelength of the complex reaches a near infrared region, the problems that the near infrared iridium (III) complex is difficult to synthesize, the absorption wavelength is relatively short and the like in the prior art are solved, and the bipyridine auxiliary ligand is incomparable with the existing bipyridine auxiliary ligand.
Disclosure of Invention
The invention aims to provide a bis-isoindole iridium (III) complex, and aims to solve the technical problems that the existing iridium (III) complex cannot achieve near infrared due to short absorption wavelength, is limited in application range and the like.
The invention also aims to provide a preparation method of the bis-isoindole iridium (III) complex, which aims to solve the technical problems that the existing preparation method of the iridium (III) complex is expensive in raw materials, harsh in reaction conditions and relatively difficult to synthesize, and the synthesized complex can not reach near infrared due to short absorption wavelength, and the like.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a bis-isoindole iridium (III) complex has a structural general formula shown as the following formula I:
wherein R is1、R2、R3Each independently selected from: H. one of an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group having 3 to 12 carbon atoms; ar (Ar)1And Ar2Each independently selected from aromatic ring containing groups.
Preferably, the structural general formula of the bis-isoindoline iridium (III) complex is shown as any one of the following formulas II to V:
wherein R is11～R13、R21～R23、R31～R33、R41～R43Each independently selected from: H. one of an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group having 3 to 12 carbon atoms; r5Selected from: H. one of aryl, alkyl with 1-12 carbon atoms and cycloalkyl with 3-12 carbon atoms; x is selected from: NCH3And O, S, CH ═ CH.
Preferably, said R is11、R13、R21、R23、R31、R33、R41、R43Each independently selected from: h or an alkyl group having 1 to 5 carbon atoms.
Preferably, said R is12、R22、R32、R42Each independently selected from: h or an alkyl group having 2 to 5 carbon atoms.
Preferably, said R is5Selected from: h or a carbazole group.
Preferably, the bis-isoindoline iridium (III) complex is selected from:
Correspondingly, the preparation method of the bis-isoindoline iridium (III) complex comprises the following steps:
under the atmosphere of a first protective gas, obtaining a mixed solution of an isoindolinone compound, a pyrrole compound and phosphorus oxychloride, and carrying out a first contact reaction to obtain a first product;
carrying out alkali treatment on the first product, and separating to obtain a bis-isoindole ligand compound;
and under the atmosphere of a second protective gas, mixing the bis-isoindole ligand compound, the iridium (III) dimer, silver hexafluorophosphate and an organic solvent, carrying out a second contact reaction, and separating to obtain a bis-isoindole iridium (III) complex.
Preferably, the conditions of the first contact reaction include: reacting for 2-100 hours in a first protective gas atmosphere at the temperature of 70-150 ℃.
Preferably, the step of subjecting the first product to an alkaline treatment comprises: adjusting the pH value of the first product to 7.5-14 by using an alkaline substance, and reacting for 1-100 hours at the temperature of 0-120 ℃.
Preferably, the conditions of the second contact reaction include: reacting for 0.5-100 hours in a second protective gas atmosphere at the temperature of 25-90 ℃.
Preferably, the molar ratio of the isoindolinone compound, the pyrrole compound and the phosphorus oxychloride is 1: (0.2-20): (1-2).
Preferably, the bis-isoindole ligand compound, the iridium (III) dimer, and the silver hexafluorophosphate are present in a molar ratio of 1: (0.45-0.5): (0.9-1).
Preferably, the alkaline substance is selected from: at least one of sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.
Preferably, the iridium (III) dimer is selected from:
Preferably, the solvent in the mixed solution is selected from: at least one of chlorobenzene, toluene and 1, 2-dichloromethane.
Preferably, the organic solvent includes: methanol and at least one of dichloroethane, chloroform, and dichloroethane.
Preferably, in the organic solvent, the ratio of the total volume of the dichloroethane, the trichloromethane and the dichloroethane to the volume of the methanol is (1-10): (1-10).
Preferably, the first shielding gas and the second shielding gas are each independently selected from the group consisting of: at least one of nitrogen and argon.
On one hand, the diisoindole iridium (III) complex provided by the invention has structural diversity, and the spatial structure torsion of the diisoindole iridium (III) complex can be adjusted by selecting the length and the type of a substituent branched chain, so that the solubility of the complex can be improved, and the optical performance of the complex can be improved; on the other hand, the compound has large conjugated bis-isoindole ligand which can further improve the optical property of the compound, so that the bis-isoindole iridium (III) compound provided by the invention has large molar absorptivity, and the molar absorptivity is up to 32200cm-1The absorption wavelength range is widened, the maximum absorption wavelength can reach 726nm in the near infrared region, the tail absorption can reach 900nm in the near infrared region, and the product can be used as a photosensitizer, an imaging reagent and strong near infrared absorptionThe receiver and the like have good application prospects in the fields of biomedicine, material science and the like.
The preparation method of the diisoindolyl iridium (III) complex provided by the invention comprises the steps of carrying out a first contact reaction on an isoindolinone compound and a pyrrole compound in the presence of phosphorus oxychloride in a protective gas atmosphere, and then carrying out alkali treatment to obtain a diindolyl ligand compound; and carrying out a second contact reaction on the obtained bis-isoindole ligand compound, an iridium (III) dimer and silver hexafluorophosphate in an organic solvent, and separating and purifying to obtain the bis-isoindole iridium (III) complex. The preparation method of the bis-isoindoline iridium (III) complex provided by the invention has the advantages that the used raw materials are commercialized, the raw materials are easy to obtain, the steps are simple, the reaction is efficient, and the synthesis yield is high. In addition, through the isoindolinone compounds and the pyrrole compounds selected from different substituents, the structure of the synthesized bis-isoindoline iridium (III) complex can be flexibly regulated and controlled, the structure diversity is realized, the optical performance can be regulated and controlled through the change of the substituents, the molar absorption coefficient is increased, and the light absorption range is widened.
Drawings
FIG. 1 shows a single crystal structure of a bis-isoindoline iridium (III) complex Ir-1 provided in example 1 of the present invention.
FIG. 2 shows the NMR spectrum of a bis-isoindoline iridium (III) complex Ir-1 provided in example 1 of the present invention.
FIG. 3 is a NMR carbon spectrum of a bis-isoindoline iridium (III) complex Ir-1 provided in example 1 of the present invention.
FIG. 4 shows the NMR spectra of a bis-isoindoline iridium (III) complex Ir-1 provided in example 1 of the present invention.
FIG. 5 shows the NMR spectra of a bis-isoindoline iridium (III) complex Ir-1 according to example 1 of the present invention.
FIG. 6 is a mass spectrum of a bis-isoindoline iridium (III) complex Ir-1 as provided in example 1 of the present invention.
FIG. 7 shows absorption spectra of bis-isoindoline iridium (III) complexes Ir-1 and Ir-7 (10. mu. mol/L) in methylene chloride, which are provided in examples 1 and 7 of the present invention.
Detailed Description
In order to make the purpose, technical solution and technical effect of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
The embodiment of the invention provides a bis-isoindole iridium (III) complex, which has a structural general formula shown as the following formula I:
wherein R is1、R2、R3Each independently selected from: H. one of an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group having 3 to 12 carbon atoms; ar (Ar)1And Ar2Each independently selected from aromatic ring containing groups.
The inventionOn one hand, the diisoindole iridium (III) complex provided by the embodiment has structural diversity, and the spatial structure torsion of the diisoindole iridium (III) complex can be adjusted by selecting the length and the type of a substituent branched chain, so that the solubility of the complex can be improved, and the optical performance of the complex can be improved; on the other hand, the compound has large conjugated bis-isoindole ligand, and the optical property of the compound can be further improved by the large conjugated bis-isoindole ligand, so that the bis-isoindole iridium (III) compound provided by the embodiment of the invention has large molar absorptivity, and the molar absorptivity is up to 32200cm-1The absorption wavelength range is widened, the maximum absorption wavelength can reach 726nm of near infrared region, the tail absorption can reach 900nm of near infrared region, and the optical fiber has good application prospect in the fields of biomedicine, material science and the like as a photosensitizer, an imaging reagent, a strong near infrared absorber and the like.
In a further embodiment, the general structural formula of the bis-isoindolyl iridium (III) complex is shown as any one of the following formulas II to V:
wherein R is11～R13、R21～R23、R31～R33、R41～R43Each independently selected from: H. one of an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group having 3 to 12 carbon atoms; r5Selected from: H. one of aryl, alkyl with 1-12 carbon atoms and cycloalkyl with 3-12 carbon atoms; x is selected from: NCH3And O, S, CH ═ CH. The diisoindolyl iridium (III) complex disclosed by the embodiment of the invention is of a symmetrical structure, so that the synthesis of the complex is facilitated, few byproducts are generated, and the synthesis efficiency is high.
In some embodiments, the bis-isoindoline iridium (III) complex has the general structural formulas II to V, wherein R is11、R13、R21、R23、R31、R33、R41、R43Each independently selected from: h or C1-5Alkyl group of (1). In other embodiments, in the general structural formulas of the bis-isoindoline iridium (III) complex formula II to formula V, R is12、R22、R32、R42Each independently selected from: h or an alkyl group having 2 to 5 carbon atoms. In other embodiments, R is5Selected from: h or a carbazole group. According to the embodiment of the invention, by further limiting the length of the substituent in the structure of the bis-isoindoline iridium (III) complex, the bis-isoindoline iridium (III) complex is effectively ensured to have better solubility and optical performance, the application is flexible and convenient, the light absorption range is wide, the near infrared can be achieved, and the molar absorption coefficient is large; and the damage of a pi conjugated system of a bis-isoindoline iridium (III) complex molecule caused by overlong branched chain of a substituent group can be avoided, and the proper pi conjugated system of the bis-isoindoline iridium (III) complex is beneficial to reducing molecular orbital transition energy, so that the absorption peak of the complex moves towards long wavelength (red shift), and the application of the bis-isoindoline iridium (III) complex in the fields of biomedicine, material science and the like is expanded.
In some embodiments, bis-isoindoline iridium (III) complexes include, but are not limited to:
The bis-isoindoline iridium (III) complex provided by the embodiment of the invention can be prepared by the following method.
Correspondingly, the embodiment of the invention also provides a preparation method of the bis-isoindole iridium (III) complex, which comprises the following steps:
s10, under the atmosphere of a first protective gas, obtaining a mixed solution of an isoindolinone compound, a pyrrole compound and phosphorus oxychloride, and carrying out a first contact reaction to obtain a first product;
s20, carrying out alkali treatment on the first product, and separating to obtain a bis-isoindole ligand compound;
s30, mixing the bis-isoindole ligand compound, the iridium (III) dimer, silver hexafluorophosphate and an organic solvent in a second protective gas atmosphere, carrying out a second contact reaction, and separating to obtain a bis-isoindole iridium (III) complex.
According to the preparation method of the diisoindolyl iridium (III) complex, the isoindolinone compound and the pyrrole compound are subjected to a first contact reaction in the presence of phosphorus oxychloride in a protective gas atmosphere, and then a diindolyl ligand compound is prepared through alkali treatment; and carrying out a second contact reaction on the obtained bis-isoindole ligand compound, an iridium (III) dimer and silver hexafluorophosphate in an organic solvent, and separating and purifying to obtain the bis-isoindole iridium (III) complex. The preparation method of the bis-isoindoline iridium (III) complex provided by the embodiment of the invention has the advantages that the used raw materials are commercialized, the raw materials are easy to obtain, the steps are simple, the reaction is efficient, and the synthesis yield is high. In addition, through the isoindolinone compounds and the pyrrole compounds selected from different substituents, the structure of the synthesized bis-isoindoline iridium (III) complex can be flexibly regulated and controlled, the structure diversity is realized, the optical performance can be regulated and controlled through the change of the substituents, the molar absorption coefficient is increased, and the light absorption range is widened.
Specifically, in the above example S10, a mixed solution of the isoindolinone compound, the pyrrole compound, and the phosphorus oxychloride is obtained under the first protective gas atmosphere, and a first contact reaction is performed, so as to obtain a first product. In the embodiment of the invention, under the atmosphere of first protective gas such as nitrogen, argon, helium and the like, isoindolinone compounds and pyrrole compounds are subjected to first contact reaction in the presence of phosphorus oxychloride, carbonyl in the isoindolinone compounds is activated by the phosphorus oxychloride, and pyrrole or derivatives thereof can be subjected to condensation reaction with the carbonyl in the isoindolinone compounds to construct C-C bonds in isoindoline so as to form the isoindoline pyrrole compounds
Wherein R is1、R2、R3、R4、R5、R6Each independently selected from: H. one of an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group having 3 to 12 carbon atoms. Wherein the protective gas atmosphere can prevent the raw material components from being oxidized, so that the components keep the reactivity.
In some embodiments, the conditions of the first contact reaction comprise: reacting for 2-100 hours in a first protective gas atmosphere at the temperature of 70-150 ℃. In the embodiment of the invention, the mixed solution of the isoindolinone compound, the pyrrole compound and the phosphorus oxychloride is reacted for 2-100 hours in the first protective gas atmosphere at the temperature of 70-150 ℃, so that the isoindolinone compound and the pyrrole compound are subjected to condensation reaction fully. If the temperature is too high or too low, the formation of by-products is increased, which is disadvantageous for the synthesis of the desired product.
In some embodiments, the molar ratio of the isoindolinone compound, the azole compound, and the phosphorus oxychloride is 1: (0.2-20): (1-2). The proportion of each raw material component in the embodiment of the invention effectively ensures the generation of the target product, and excessive or insufficient certain component can increase byproducts in the reaction process.
In some embodiments, under the first protective gas of at least one of nitrogen, argon and helium, the molar ratio of the isoindolinone compound, the pyrrole compound and the phosphorus oxychloride is 1: (0.2-20): (1-2) reacting the mixed solution of the isoindolinone compound, the pyrrole compound and the phosphorus oxychloride for 2-100 hours in a first protective gas atmosphere at the temperature of 70-150 ℃ to obtain a first product.
Specifically, in step S20, the first product is subjected to alkali treatment and isolated to obtain a bis-isoindole ligand compound. In the embodiment of the invention, the first product is subjected to alkali treatment, so that the unstable isoindole pyrrole structure in the first product is dimerized under an alkaline condition to form a double isoindole ligand compound.
In some embodiments, the step of subjecting the first product to an alkaline treatment comprises: adjusting the pH value of the first product to 7.5-14 by using an alkaline substance, and reacting for 1-100 hours at the temperature of 0-120 ℃. In some embodiments, the alkaline material is selected from: at least one of sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide. According to the embodiment of the invention, the pH of the first product is adjusted to be 7.5-14 alkaline through alkaline substances such as sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide, and then the first product is reacted for 1-100 hours at the temperature of 0-120 ℃, so that the unstable isoindole pyrrole structure in the first product is fully dimerized under the alkaline condition, and the double isoindole ligand compound is formed. In some embodiments, the step of alkali treatment of the first product may also be performed by adding a small amount of potassium ferricyanide to shorten the reaction time, and performing extraction separation and purification with dichloromethane, chloroform, water, etc. after the alkali treatment to obtain the bis-isoindole ligand compound.
Specifically, in step S30, the bis-isoindole ligand compound, the iridium (III) dimer, and silver hexafluorophosphate are mixed with an organic solvent in a second protective gas atmosphere, and then subjected to a second contact reaction, followed by separation to obtain a bis-isoindole iridium (III) complex. Hair brushIn the second contact reaction, the bis-isoindole ligand compound, the iridium (III) dimer and the silver hexafluorophosphate are mixed with an organic solvent in a second protective gas atmosphere of nitrogen, argon, helium and the like, wherein the silver hexafluorophosphate and Cl in the iridium (III) dimer form AgCl precipitate, the iridium (III) dimer is depolymerized and reacts with the bis-isoindole ligand mixture to form Ir (III) cations; in addition, PF is provided at the same time6 -Novel Ir (III) complexes of anions with bis-isoindolylium (III). Wherein the protective gas atmosphere can prevent the raw material components from being oxidized, so that the components keep the reactivity.
In some embodiments, the conditions of the second contact reaction comprise: reacting for 0.5-100 hours in a second protective gas atmosphere at the temperature of 25-90 ℃. In the embodiment of the invention, the bis-isoindole ligand compound, the iridium (III) dimer, the silver hexafluorophosphate and the organic solvent are mixed and then react for 0.5 to 100 hours in a second protective gas atmosphere at the temperature of 25 to 90 ℃. In some embodiments, the bis-isoindole ligand compound, the iridium (III) dimer, and the silver hexafluorophosphate are in a molar ratio of 1: (0.45-0.5): (0.9-1). According to the embodiment of the invention, the proportion of the bis-isoindole ligand compound, the iridium (III) dimer and the silver hexafluorophosphate is reasonably regulated and controlled, the temperature and the reaction time are reflected, the generation of byproducts is reduced, the synthesis efficiency is improved, and the separation and purification difficulty is reduced.
In some embodiments, the iridium (III) dimer is selected from:
In some embodiments, the organic solvent comprises: methanol and at least one of dichloroethane, chloroform, and dichloroethane. In some embodiments, the ratio of the total volume of the dichloroethane, the trichloromethane, and the dichloroethane to the volume of the methanol is (1-10): (1-10). The embodiment of the invention adopts the organic solvent consisting of methanol and at least one of dichloroethane, trichloromethane and dichloroethane, not only ensures the solubility of the bis-isoindoline ligand compound, the iridium (III) dimer and the silver hexafluorophosphate in the solvent, but also can adjust the boiling point of the solution, is beneficial to full reaction among substance components and improves the synthesis efficiency of the bis-isoindoline iridium (III) complex.
In some embodiments, the bis-isoindoline ligand compound, the iridium (III) dimer, and the silver hexafluorophosphate are present in a molar ratio of 1: (0.45-0.5): (0.9-1), mixing the bis-isoindole ligand compound, the iridium (III) dimer, silver hexafluorophosphate and an organic solvent consisting of methanol and at least one of dichloroethane, chloroform and dichloroethane, reacting for 0.5-100 hours in a second protective gas atmosphere at the temperature of 25-90 ℃, and separating to obtain the bis-isoindole iridium (III) complex.
In order to make the details of the above-mentioned implementation and operation of the present invention clearly understandable to those skilled in the art and to make the progress of the bis-isoindole iridium (III) complex and the preparation method thereof obvious, the technical solutions are illustrated by the following examples.
Example 1
Synthesis of a bis-isoindoline iridium (III) complex Ir-1:
isoindolinone (100mg, 0.75mmol) and pyrrole (62. mu.L, 0.90mmol) were dissolved in anhydrous chlorobenzene (20mL) under nitrogen, phosphorus oxychloride (68. mu.L, 0.75mmol) was added, and the reaction mixture was heated to 110 ℃ and stirred for 6 h. And (3) performing TLC tracing on a point plate, adding a sodium carbonate saturated solution containing potassium ferricyanide into the reaction system after the isoindolinone is completely consumed, continuously stirring at room temperature for 2 hours, then transferring the reaction mixture into a separating funnel, adding dichloromethane and water, extracting, standing, separating an organic phase, extracting a corresponding water phase with dichloromethane for three times, and combining organic layers. The organic phase was washed once with water, dried over anhydrous sodium sulfate, filtered, the solvent was concentrated under vacuum, and purified by silica gel column chromatography to give 54 mg. 54mg (0.15mmol) of the obtained diisoindole ligand powder, 0.075mmol and 81mg of iridium (III) dimer Ir dimer 1 and 38mg of silver hexafluorophosphate are stirred for 2 hours at 80 ℃ in a system (the total volume is 20mL) with 1:1 ratio of methanol and 1, 2-dichloroethane to obtain a target product, the target product is purified by silica gel column chromatography, and then the diisoindole iridium (III) complex powder Ir-1 is obtained by recrystallization with dichloromethane and n-hexane, and the yield is 58% (87 mg). The X-ray single crystal diffraction pattern is shown in figure 1.
The nuclear magnetic data and the high-resolution mass spectrum data of the diisoindolyl iridium (III) complex powder Ir-1 are as follows:
1H NMR(400MHz,CD3CN) δ 9.21(s,2H),8.68(d, J ═ 7.9Hz,2H),8.44(d, J ═ 6.4Hz,2H),8.04(d, J ═ 7.8Hz,2H),7.93(d, J ═ 8.2Hz,2H), 7.85-7.73 (m,4H),7.62(t, J ═ 7.6Hz,2H),7.56(d, J ═ 7.8Hz,2H),7.02(t, J ═ 6.6Hz,2H),6.96(s,2H),6.88(t, J ═ 7.6Hz,2H),6.75(t, J ═ 7.4Hz,2H), 6.54-6.45 (m,2H),6.19(d, J ═ 6.9, 2H),6.09(d, J ═ 4H, 2H), 2H, 6.09 (H), and fig. 3.6.7.6.6.6.6.6.6.6.6.6 Hz, 2H.
13C NMR(101MHz,CD3CN) δ 167.9,161.0,151.8,151.7,148.0,145.4,141.5,139.5,135.9,132.9,131.9,131.7,131.1,128.1,126.1,126.0,126.0,124.2,123.6,122.9,120.6,120.5,112.7, as shown in fig. 3.
19F NMR(376MHz,CD3CN) δ -70.38(d, J ═ 7.5Hz,6F).
31P NMR(162MHz,CD3CN) delta (-130.05) - (-156.22) (m, P) as shown in figure 5.
HRMS(ESI)calcd for C46H32IrN6[M–PF6]+861.2312 and found 861.2334, as shown in figure 6.
Example 2
Synthesis of a bis-isoindoline iridium (III) complex Ir-2:
54mg (0.15mmol) of the diindolyl ligand powder obtained in example 1, 0.075mmol and 96mg of iridium (III) dimer Ir dimer 2 and 0.15mmol and 38mg of silver hexafluorophosphate are put in a system (total volume is 20mL) with the ratio of 1:1 of methanol and 1, 2-dichloroethane, and stirred for 2h at 80 ℃ to obtain a target product, which is purified by silica gel column chromatography, and then recrystallized by dichloromethane and n-hexane to obtain diindolyl iridium (III) complex powder Ir-2 with the yield of 47% (78 mg).
The nuclear magnetic data and the high-resolution mass spectrum data of the bis-isoindoline iridium (III) complex Ir-2 are as follows:
1H NMR(400MHz,CD3CN)δ9.27(s,2H),8.67(dd,J＝6.5,3.5Hz,2H),8.55(d,J＝7.9Hz,2H),8.21(d,J＝6.4Hz,2H),8.10(d,J＝8.1Hz,2H),7.95(d,J＝7.9Hz,2H),7.86(dd,J＝6.5,3.2Hz,2H),7.76–7.66(m,7H),7.52(t,J＝7.7Hz,2H),7.35(d,J＝6.4Hz,2H),7.01(t,J＝7.6Hz,2H),6.89(s,2H),6.78(t,J＝7.4Hz,2H),6.48(s,2H),6.41(d,J＝7.5Hz,2H),6.18–6.07(m,2H).
13C NMR(101MHz,CD3CN)δ168.3,159.4,150.5,149.8,145.7,141.7,140.4,137.1,134.9,132.5,131.9,131.2,131.1,130.8,130.5,128.9,127.8,127.4,126.6,126.2,125.3,124.9,122.9,121.8,121.8,120.0,112.4.
31P NMR(162MHz,CD3CN)δ(-129.60)–(-156.01)(m,P).19F NMR(376MHz,CD3CN)δ-70.42(d,J＝7.6Hz,6F).
HRMS(ESI)calcd for C54H36IrN6[M–PF6]+:961.2625,found 961.2625.
example 3
Synthesis of a bis-isoindoline iridium (III) complex Ir-3:
the procedure of example 2 was followed, except that an equivalent amount of iridium (III) dimer was changed to Ir dimer 3, to prepare Ir-3 in a yield of 31% (56 mg).
The nuclear magnetic data and the high-resolution mass spectrum data of the bis-isoindoline iridium (III) complex Ir-3 are as follows:
1H NMR(400MHz,CD3CN)δ9.43(s,2H),8.54(d,J＝7.9Hz,2H),8.47(d,J＝6.3Hz,2H),7.85(d,J＝8.0Hz,2H),7.75–7.68(m,8H),7.57(d,J＝8.4Hz,4H),7.51–7.45(m,4H),7.38(d,J＝6.5Hz,2H),7.25–7.19(m,4H),7.11(d,J＝8.3Hz,2H),7.01(d,J＝8.3Hz,2H),6.54(s,2H),6.45(s,2H),5.84(d,J＝4.1Hz,2H).
13C NMR(101MHz,CD3CN)δ160.8,144.2,141.0,139.1,137.8,135.2,133.5,133.4,132.8,132.0,131.7,131.6,130.8,130.4,129.6,127.2,127.1,126.7,126.5,126.0,126.0,125.5,125.2,124.2,122.2,121.0,120.1,118.3,112.4.
31P NMR(162MHz,CD3CN)δ(-130.06)–(-156.23)(m,P).19F NMR(376MHz,CD3CN)δ-70.39(d,J＝7.5Hz,6F).
HRMS(ESI)calcd for C62H40IrN6[M–PF6]+:1061.2938,found 1061.2941.
example 4
Synthesis of a bis-isoindoline iridium (III) complex Ir-4:
the procedure of example 2 was followed, except that an equivalent amount of iridium (III) dimer was changed to Ir dimer 4, to prepare Ir-4 in a yield of 45% (96 mg).
The nuclear magnetic data and the high-resolution mass spectrum data of the bis-isoindoline iridium (III) complex Ir-4 are as follows:
1H NMR(400MHz,CD2Cl2)δ9.24(s,2H),8.75(d,J＝8.6Hz,2H),8.56(dd,J＝8.2,3.3Hz,4H),8.23(d,J＝6.4Hz,2H),7.98(t,J＝7.3Hz,6H),7.75(dq,J＝11.8,6.5Hz,10H),7.60–7.55(m,4H),7.29–7.22(m,6H),7.20–7.13(m,6H),7.05(s,2H),6.88(d,J＝2.2Hz,2H),6.77(s,2H),6.40(dd,J＝4.1,2.2Hz,2H).
13C NMR(101MHz,CD2Cl2)δ167.9,160.3,152.5,151.1,144.9,141.8,141.7,140.5,139.5,137.6,135.0,132.7,131.8,131.5,130.8,129.7,128.1,127.4,126.9,126.5,126.5,125.7,125.5,124.3,124.0,122.3,122.2,121.0,120.8,120.6,113.6,110.5.
31P NMR(162MHz,CD2Cl2)δ(-130.05)–(-156.22)(m,P).19F NMR(376MHz,CD2Cl2)δ-70.80(d,J＝7.6Hz,6F).
HRMS(ESI)calcd for C78H50IrN6[M–PF6]+:1291.3782,found 1291.3793.
example 5
Synthesis of a bis-isoindoline iridium (III) complex Ir-5:
the procedure of example 2 was followed, except that an equivalent amount of iridium (III) dimer was changed to Ir dimer 5, to prepare Ir-5 in a yield of 29% (44 mg).
The nuclear magnetic data and the high-resolution mass spectrum data of the bis-isoindoline iridium (III) complex Ir-5 are as follows:
1H NMR(400MHz,CD2Cl2)δ9.09(s,2H),8.70(d,J＝7.9Hz,2H),8.12(d,J＝7.9Hz,2H),8.08(d,J＝5.8Hz,2H),7.79(t,J＝7.6Hz,2H),7.67(dt,J＝15.0,7.8Hz,5H),7.58(d,J＝8.0Hz,2H),7.34(d,J＝4.8Hz,2H),7.24(s,2H),6.83(ddd,J＝7.4,6.0,1.4Hz,2H),6.69(s,2H),6.30(dt,J＝4.5,2.4Hz,2H),6.04(d,J＝4.8Hz,2H).
13C NMR(101MHz,CD2Cl2)δ163.9,160.4,151.0,150.9,146.9,140.9,139.6,137.4,135.6,131.7,131.4,131.2,131.1,128.3,126.0,125.5,123.0,121.3,121.2,119.2,113.3.31P NMR(162MHz,CD2Cl2)δ(-129.87)–(-156.19)(m,P).
19F NMR(376MHz,CD2Cl2)δ-74.46(d,J＝7.5Hz,6F).
HRMS(ESI)calcd for C42H28IrN6S2[M–PF6]+:873.1441,found 873.1440.
example 6
Synthesis of a bis-isoindoline iridium (III) complex Ir-6:
the procedure of example 2 was followed, except that an equivalent amount of iridium (III) dimer was changed to Ir dimer 6, to prepare Ir-6 in a yield of 66% (104 mg).
The nuclear magnetic data and the high-resolution mass spectrum data of the bis-isoindoline iridium (III) complex Ir-6 are as follows:
1H NMR(400MHz,CD2Cl2)δ9.39(d,J＝5.2Hz,2H),8.96(s,2H),8.72(d,J＝7.9Hz,2H),8.57(d,J＝5.3Hz,2H),8.35(dd,J＝12.6,7.8Hz,4H),8.01(d,J＝7.9Hz,2H),7.83–7.72(m,10H),7.63–7.57(m,4H),7.44(dd,J＝10.6,2.8Hz,5H),7.28–7.21(m,4H),7.00(t,J＝7.6Hz,2H),6.95(s,2H),6.84(t,J＝7.6Hz,3H),6.17(s,3H),6.03(d,J＝3.8Hz,2H),5.97(d,J＝7.2Hz,2H),5.91(d,J＝7.4Hz,2H).
13C NMR(101MHz,CD2Cl2)δ160.6,158.5,157.4,151.4,151.3,149.9,143.2,141.5,141.4,141.0,138.1,136.4,135.8,135.2,134.2,131.5,131.3,130.4,130.1,129.8,129.4,129.1,128.1,128.0,127.3,127.2,125.8,125.4,124.9,124.2,122.8,122.4,122.4,121.9,120.6,119.9,112.9.31P NMR(162MHz,CD2Cl2)δ(-129.82)–(-156.15)(m,P).
19F NMR(376MHz,CD2Cl2)δ-74.15(d,J＝7.6Hz,6F).
HRMS(ESI)calcd for C50H32IrN6[M–PF6]+:909.2312,found 909.2327.
example 7
Synthesis of a bis-isoindoline iridium (III) complex Ir-7:
the procedure of example 2 was followed, except that pyrrole was replaced by equivalent of 2, 4-dimethyl-3-ethylpyrrole and ethyl by equivalent of iridium (III) dimer to Ir dimer 1, to prepare Ir-7 in 51% yield (85 mg).
The nuclear magnetic data and the high-resolution mass spectrum data of the bis-isoindoline iridium (III) complex Ir-7 are as follows:
1H NMR(400MHz,CDCl3)δ8.55(d,J＝7.9Hz,2H),8.33–8.22(m,2H),7.83–7.73(m,4H),7.69(t,J＝7.5Hz,2H),7.60(d,J＝7.7Hz,2H),7.48(t,J＝7.5Hz,2H),7.39(s,2H),7.34(d,J＝7.2Hz,2H),7.16–7.05(m,2H),6.66(t,J＝7.8Hz,2H),6.52(t,J＝7.4Hz,2H),5.93(d,J＝7.4Hz,2H),2.14(q,J＝7.5Hz,4H),1.81(s,6H),1.77(s,6H),0.95(t,J＝7.5Hz,6H).
13C NMR(101MHz,CDCl3)δ168.3,161.9,150.4,149.7,149.0,143.1,141.1,138.1,134.8,133.3,131.2,130.7,130.2,129.3,126.3,126.3,126.1,124.7,123.8,122.9,121.6,119.1,118.8,17.6,14.7,12.0,11.9.
31P NMR(162MHz,CDCl3)δ(-129.77)–(-156.18)(m,P).19F NMR(376MHz,CDCl3)δ-74.15(d,J＝7.6Hz,6F).
HRMS(ESI)calcd for C54H48IrN6[M–PF6]+:973.3564,found 973.3566.
further, in order to verify the advancement of the bis-isoindoline iridium (III) complex prepared by the examples of the present invention, the examples of the present invention were subjected to performance tests.
Test example 1
In the test example of the invention, the diisoindole iridium (III) complexes Ir-1 to Ir-7 prepared in examples 1 to 7 are respectively tested in dichloromethane and acetonitrile for the maximum absorption wavelength, the molar absorption coefficient and the log value (A) thereof, and the test results are shown in the following table 1:
TABLE 1
In addition, the absorption spectra of the bis-isoindole iridium (III) complex Ir-1 and Ir-7 (10. mu. mol/L) prepared in examples 1 and 7 in dichloromethane are shown in a figure 7, and the electron donating capability of 2, 4-dimethyl-3-ethylpyrrole in the bis-isoindole iridium (III) complex Ir-7 is greatly enhanced compared with that of unsubstituted pyrrole, so that a stronger electron pushing and pulling effect is formed, and the spectrum can be effectively red-shifted.
From the test results, the bis-isoindolyl iridium (III) complex prepared in the embodiments 1 to 7 has structural diversity, can be realized by substituent group change, has adjustable spectrum, large molar absorption coefficient (up to 25500cm < -1 >), maximum absorption wavelength of 710nm in the near infrared region and tail absorption of 900nm, and has good application prospect in the fields of biomedicine, material science and the like. In addition, the preparation method provided by the embodiment of the invention has the advantages of easily available raw materials, simple process, high reaction efficiency and high yield.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A bis-isoindole iridium (III) complex is characterized in that the structural general formula of the bis-isoindole iridium (III) complex is shown as the following formula I:
wherein R is1、R2、R3Each independently selected from: H. one of an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group having 3 to 12 carbon atoms; ar (Ar)1And Ar2Each independently selected from aromatic ring containing groups.
2. The bis-isoindole iridium (III) complex of claim 1, wherein the bis-isoindole iridium (III) complex has a general structural formula as shown in any one of formulas II to V below:
wherein R is11～R13、R21～R23、R31～R33、R41～R43Each independently selected from: H. one of an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group having 3 to 12 carbon atoms; r5Selected from: H. one of aryl, alkyl with 1-12 carbon atoms and cycloalkyl with 3-12 carbon atoms; x is selected from: NCH3And O, S, CH ═ CH.
3. The iridium (III) bis-isoindole complex of claim 2, wherein R is11、R13、R21、R23、R31、R33、R41、R43Each independently selected from: h or alkyl with 1-5 carbon atoms; and/or the presence of a gas in the gas,
the R is12、R22、R32、R42Each independently selected from: h or alkyl with 2-5 carbon atoms; and/or the presence of a gas in the gas,
the R is5Selected from: h or a carbazole group.
4. The bis-isoindole iridium (III) complex of any of claims 1 to 3, wherein the bis-isoindole iridium (III) complex is selected from the group consisting of:
5. A preparation method of a bis-isoindole iridium (III) complex is characterized by comprising the following steps:
under the atmosphere of a first protective gas, obtaining a mixed solution of an isoindolinone compound, a pyrrole compound and phosphorus oxychloride, and carrying out a first contact reaction to obtain a first product;
carrying out alkali treatment on the first product, and separating to obtain a bis-isoindole ligand compound;
and under the atmosphere of a second protective gas, mixing the bis-isoindole ligand compound, the iridium (III) dimer, silver hexafluorophosphate and an organic solvent, carrying out a second contact reaction, and separating to obtain a bis-isoindole iridium (III) complex.
6. The process for preparing bis-isoindoline iridium (III) complex of claim 5, wherein the conditions of the first contacting reaction comprise: reacting for 2-100 hours in a first protective gas atmosphere at the temperature of 70-150 ℃; and/or the presence of a gas in the gas,
the step of subjecting the first product to an alkaline treatment comprises: adjusting the pH value of the first product to 7.5-14 by using an alkaline substance, and reacting for 1-100 hours at the temperature of 0-120 ℃; and/or the presence of a gas in the gas,
the conditions of the second contact reaction include: reacting for 0.5-100 hours in a second protective gas atmosphere at the temperature of 25-90 ℃.
7. The process for preparing iridium (III) bis (isoindolinone) complex according to claim 6, wherein the molar ratio of isoindolinone compound, pyrrole compound and phosphorus oxychloride is 1: (0.2-20): (1-2); and/or the presence of a gas in the gas,
the bis-isoindole ligand compound, the iridium (III) dimer, and the silver hexafluorophosphate are present in a molar ratio of 1: (0.45-0.5): (0.9-1).
8. The process for the preparation of bis-isoindoline iridium (III) complexes according to claim 6 or 7, wherein the basic substance is selected from the group consisting of: at least one of sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide; and/or the presence of a gas in the gas,
the iridium (III) dimer is selected from:
9. The process for preparing bis-isoindoline iridium (III) complex according to claim 8, wherein the solvent in the mixed solution is selected from the group consisting of: at least one of chlorobenzene, toluene, 1, 2-dichloromethane; and/or the presence of a gas in the gas,
the organic solvent includes: methanol and at least one of dichloroethane, chloroform, and dichloroethane.
10. The process for preparing bis-isoindoline iridium (III) complex according to claim 9, wherein the ratio of the total volume of dichloroethane, chloroform, and dichloroethane to the volume of methanol in the organic solvent is (1 to 10): (1-10); and/or the presence of a gas in the gas,
the first shielding gas and the second shielding gas are each independently selected from the group consisting of: at least one of nitrogen and argon.
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