D-A type covalent organic framework based on asymmetric benzothiadiazole ligand as well as preparation method and application of D-A type covalent organic framework

Abstract

The invention relates to the technical field of photocatalysis, in particular to a D-A type covalent organic framework based on an asymmetric benzothiadiazole ligand and a preparation method and application of the D-A type covalent organic framework. According to the D-A type covalent organic framework provided by the invention, asymmetric benzothiadiazole ligands and 1, 3, 6, 8-tetra (4-aminophenyl) pyrene are used as main body structures, double pi bridges are used for connection, a D-pi-pi-A structure is constructed, and the pi bridges are expanded, so that the band gap of a framework material is effectively reduced, the delocalization capability of charges is improved, the charge transmission efficiency is improved, and the potential safety hazard is reduced. Further, the high photocatalytic activity is improved.

Description

Technical Field

[0001] The invention relates to the technical field of photocatalysis, and in particular to a DA-type covalent organic framework based on an asymmetric benzothiadiazole ligand, and a preparation method and application thereof. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention, and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.

[0003] Covalent organic frameworks (COFs) are a type of organic porous polymers with periodicity formed by connecting their organic building blocks with light elements (C, H, O, B, N, etc.) through covalent bonds. Therefore, they have many unique properties, such as rigid structure, high thermal stability, large specific surface area, tunable structure, periodic π array and porous structure. They are now widely used in guest molecule adsorption, energy storage materials, gas storage and separation, heterogeneous photocatalysis, sensing and drug delivery, etc., showing great development potential.

[0004] The introduction of donor-acceptor (DA) structure into covalent organic frameworks is beneficial to reduce the exciton binding energy, promote the separation and transfer of photogenerated carriers, and thus improve the photocatalytic performance of covalent organic frameworks. The benzothiadiazole unit has unique electron-deficient characteristics and a planar conjugated structure, which can be introduced into the covalent organic framework structure to prepare high-performance donor (D)-acceptor (A) type covalent organic framework photocatalysts. However, the charge transfer efficiency of conventional benzothiadiazole-based covalent organic frameworks is still limited by the localized π electron distribution and limited exciton dissociation channels, which in turn affects the photocatalytic performance. Therefore, it is urgent to solve the charge transfer efficiency of benzothiadiazole-based covalent organic frameworks and improve their photocatalytic performance. Summary of the invention

[0005] In order to overcome the above problems, the present invention provides a DA-type covalent organic framework based on an asymmetric benzothiadiazole ligand, and a preparation method and application thereof.

[0006] In order to achieve the above technical objectives, the present invention adopts the following technical solutions: In the first aspect of the present invention, there is provided a DA-type covalent organic framework based on an asymmetric benzothiadiazole ligand, which has the structure shown in formula (I) as a structural repeating unit;

[0007] Formula (I).

[0008] The second aspect of the present invention provides an asymmetric benzothiadiazole ligand for constructing the DA-type covalent organic framework based on the asymmetric benzothiadiazole ligand described in the first aspect, and its structural formula is shown in formula (II);

[0009] Formula (II).

[0010] The third aspect of the present invention provides a method for preparing the DA-type covalent organic framework based on the asymmetric benzothiadiazole ligand described in the first aspect, comprising the following steps: The asymmetric benzothiadiazole ligand shown in formula (II) and 1,3,6,8-tetrakis(4-aminophenyl)pyrene are dissolved in an organic solvent, acetic acid is added as a catalyst, and a DA-type covalent organic framework based on the asymmetric benzothiadiazole ligand is synthesized by solvothermal reaction.

[0011] In one or more embodiments, the molar ratio of the asymmetric benzothiadiazole ligand represented by formula (II) to 1,3,6,8-tetrakis(4-aminophenyl)pyrene is (1.5-3):1, preferably 2:1.

[0012] In one or more embodiments, the organic solvent is a mixed solution of o-dichlorobenzene and anhydrous ethanol.

[0013] Preferably, the volume ratio of o-dichlorobenzene to anhydrous ethanol is (2.5-4):1, preferably 3:1.

[0014] In one or more embodiments, the concentration of the asymmetric benzothiadiazole ligand represented by formula (II) in the organic solvent is 0.04-0.08 mol / L, preferably 0.05 mol / L.

[0015] In one or more embodiments, the temperature of the solvothermal reaction is 100-150° C., preferably 120° C.; the time of the solvothermal reaction is 60-80 h, preferably 72 h.

[0016] The fourth aspect of the present invention provides the use of the DA-type covalent organic framework based on asymmetric benzothiadiazole ligands described in the first aspect or the DA-type covalent organic framework based on asymmetric benzothiadiazole ligands prepared by the preparation method described in the third aspect as a photocatalyst.

[0017] In one or more embodiments, the application includes: catalytic oxidation of sulfide to synthesize sulfoxide.

[0018] In one or more embodiments, the application includes: catalytic oxidation of tetrahydroisoquinoline compounds to synthesize isoquinolone compounds.

[0019] The beneficial effects of the present invention are: (1) The present invention relates to the field of photocatalysis technology, and specifically to a DA-type covalent organic framework based on an asymmetric benzothiadiazole ligand, and a preparation method and application thereof. The DA-type covalent organic framework provided by the present invention has an asymmetric benzothiadiazole ligand and 1,3,6,8-tetrakis(4-aminophenyl)pyrene as the main structure, and is connected by a double π bridge to construct a D-π-π-A structure. The structural design of the π bridge extension effectively reduces the band gap of the framework material, improves the charge delocalization ability, improves the charge transfer efficiency, and thus improves the high photocatalytic activity.

[0020] (2) The DA-type covalent organic framework based on asymmetric benzothiadiazole ligand provided by the present invention can efficiently photocatalytically oxidize anisyl sulfide substrates to synthesize anisyl sulfoxide products with a yield of more than 90%; and can photocatalytically oxidize more difficult-to-oxidize tetrahydroisoquinoline compounds to synthesize isoquinolone compounds with a yield of more than 70%. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The accompanying drawings in the specification, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0022] Figure 1 is the H NMR spectrum of the asymmetric benzothiadiazole ligand; Figure 2 The powder X-ray diffraction pattern of the DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligand; Figure 3 The structural diagram of the DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligand simulated by Materials Studio software; Figure 4 Fourier transform infrared (FT-IR) spectrum of the DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligand; Figure 5 The DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligands 13 C CP / MASNMR spectra; Figure 6 The N-terminal structure of the DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligands 2 Adsorption-desorption isotherm diagram, in which the inset is the pore size distribution diagram; Figure 7 Solid-state UV-visible absorption spectrum of DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligand; Figure 8 The Tauc band gap of the DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligands; Fig. 9 Cyclic voltammogram of DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligand; Fig.10 Electrochemical impedance spectroscopy of the DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligands; Fig.11 The photocurrent response signal of the DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligand; Fig.12 is the H NMR spectrum of the product after catalytic oxidation of substrate 1a; Fig.13 is the H NMR spectrum of the product after catalytic oxidation of substrate 1b; Fig.14 This is the H NMR spectrum of the product after catalytic oxidation of substrate 1c; Fig.15 is the H NMR spectrum of the product after catalytic oxidation of substrate 1d; Fig.16 is the H NMR spectrum of the product after catalytic oxidation of substrate 1e; Fig.17 The powder X-ray diffraction pattern of the DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligand after repeated use for 5 times; Fig.18 is the H NMR spectrum of the product after catalytic oxidation of substrate 2a; Fig.19 is the H NMR spectrum of the product after catalytic oxidation of substrate 2b; Fig. 20 is the H NMR spectrum of the product after catalytic oxidation of substrate 2c; Fig.21 is the H NMR spectrum of the product after catalytic oxidation of substrate 2d; Fig. 22 This is the H NMR spectrum of the product after catalytic oxidation of substrate 2e. DETAILED DESCRIPTION

[0023] It should be noted that the following detailed descriptions are exemplary and are intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0024] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprising" and / or "including" are used in this specification, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.

[0025] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in conjunction with specific embodiments.

[0026] Example 1 Preparation of unsymmetrical benzothiadiazole ligands: 0.5 mmol 7-(4-formylphenyl)-4-formylbenzo[c][1,2,5]thiadiazole (PBT), 1.1 mmol ((1,3-dioxolan-2-yl)methyl)tributylphosphine bromide (cas:115754-62-6) and 2.5 mmol sodium hydride (cas:7646-69-7, 60% dispersed in kerosene) were dispersed in 10 mL tetrahydrofuran and reacted at room temperature for 16 hours. After the reaction was completed, 3-4 mL 10% hydrochloric acid aqueous solution was added to the above reaction solution, and the reaction solution was adjusted to be acidic and stirred for 4 hours. Saturated sodium bicarbonate aqueous solution was added, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the solvent was evaporated to obtain a crude product. The obtained crude product was purified by silica gel chromatography (eluent ratio of dichloromethane: ethyl acetate (v / v) = 50:1) to finally obtain an orange powder asymmetric benzothiadiazole ligand (PBT-v), i.e., the compound shown in formula (II) (C 18 H 12 N 2 O 2 S, yield about 77%), its H NMR spectrum is as follows Figure 1 shown. 1 H NMR (CDCl 3 , 400 MHz): δ (ppm) 9.81-9.79(d, J = 8.0 Hz, 1H)9.71-9.69(d, J = 8.0 Hz, 1H)8.02-8.00(d, J = 8.0 Hz, 2H)7.88-7.85 (m, J = 12.0 Hz, 2H)7,78-7.77(d, J = 4.0 Hz, 1H)7.71-7.68(d, J= 12.0 Hz, 2H)7.61-7.52 (m, J = 28.0 Hz,1H)7.52-7.48 (m, J = 12.0 Hz, 1H)6.78-6.72 (m, J = 24.0 Hz, 1H).

[0027] Example 2 Preparation of DA-type covalent organic frameworks based on asymmetric benzothiadiazole ligands: 0.04 mmol asymmetric benzothiadiazole ligand (PBT-v), 0.02 mmol 1,3,6,8-tetrakis(4-aminophenyl)pyrene (TPPy, cas: 1610471-69-6), 750 μL o-dichlorobenzene and 250 μL anhydrous ethanol were added into a Pyrex tube in sequence. After ultrasonication for 5 min, 100 μL of 6 mol∙L -1 Acetic acid. Freeze the glass tube with liquid nitrogen, thaw and vacuum degas, repeat three times, seal the glass tube, and heat it in a 120 ℃ oven for 72 hours. After cooling, a reddish-brown precipitate is obtained, which is thoroughly washed with anhydrous ethanol, N,N-dimethylformamide and dichloromethane, filtered, and vacuum dried at 120 ℃ for 12 hours to obtain a reddish-brown powder, which is the DA-type covalent organic framework TPPy-PBT-COF-v (C 80 H 48 N 8 S 2 , yield about 93%).

[0028] Figure 2 Powder X-ray diffraction (PXRD) pattern of the DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligands. Figure 3 The structural diagram of the DA-type covalent organic framework TPPy-PBT-COF-v of the asymmetric benzothiadiazole ligand simulated by Materials Studio software. According to the experimental powder X-ray diffraction pattern (PXRD) and the structure simulated by Materials Studio software, it is shown that the DA-type covalent organic framework TPPy-PBT-COF-v of the asymmetric benzothiadiazole ligand is an ordered framework structure. The PXRD of TPPy-PBTP-COF-v has diffraction peaks at 2.71°, 3.82°, 5.45° and 8.13°, corresponding to the crystal planes (110), (200), (220) and (330), respectively. The simulated structure of TPPy-PBTP-COF-v is: monoclinic system, space group is P2 , unit cell parameters a = 46.507 Å,b = 45.653 Å, c = 3.549 Å, α = β = γ =90º. The residual and contour differences between PXRD and the AA stacking model of the simulated structure are small ( R wp = 6.15%, R p = 3.97%), indicating that TPPy-PBTP-COF-v is stacked layer by layer in an AA stacking manner.

[0029] Figure 4 The Fourier transform infrared (FT-IR) spectrum of the DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligands. Comparative analysis shows that in the infrared spectrum of TPPy-PBT-COF-v, the NH stretching vibration peak (3325 cm -1 、3347 cm -1 ) and the C=O stretching vibration peak of PBT-v at 1664 cm -1 disappears, and at 1614 cm -1 and 3029 cm -1 The appearance of C=N and C=CH peaks at 370 nm indicated the successful polymerization to form a crystalline covalent organic framework.

[0030] Figure 5 The DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligands 13 C CP / MAS NMR spectrum. The chemical shift of TPPy-PBT-COF-v at 156 ppm is attributed to the imine carbon, the peaks at 151 ppm and 145 ppm are the carbon on the benzothiadiazole unit, and the broad peak at 140-112 ppm is the aromatic carbon. This also indicates that the polymerization was successful to form a covalent organic framework with high crystallinity.

[0031] Figure 6 The N-terminal structure of the DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligands 2 Adsorption-desorption isotherms and pore size distribution (inset). N 2 According to the adsorption-desorption measurements, TPPy-PBT-COF-v exhibited a typical type IV isotherm with a surface area of ​​2321.94 m 2 g -1The pore center is 2.88 nm, indicating that it is a mesoporous material, which once again proves that TPPy-PBT-COF-v is an AA-type layer-by-layer stacking structure.

[0032] Figure 7 Solid-state UV-visible absorption spectrum of DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligand. Figure 7 It can be seen that TPPy-PBT-COF-v has a wide light absorption range, which can be red-shifted to around 800 nm.

[0033] Figure 8 The Tauc band gap of the DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligands. Figure 8 It can be calculated that TPPy-PBT-COF-v has a smaller band gap, which is 1.71 eV.

[0034] Fig. 9 The cyclic voltammogram of the DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligands is shown in Figure 2. The reduction potential of TPPy-PBT-COF-v was measured by cyclic voltammetry (CV). The reduction potential was -0.69 eV and the highest occupied molecular orbital (HOMO) was -4.11 eV. Figure 8 It can be seen that its Tauc band gap is 1.71 eV, and its lowest unoccupied molecular orbital (LUMO) is -5.82 eV.

[0035] Fig.10 Electrochemical impedance spectroscopy of the DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligands. Fig.11 The photocurrent response signal of the DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligand.

[0036] The structure of the covalent organic framework TPPy-PBT-COF for comparison is shown below: ; The structure of the covalent organic framework TPPy-PBT-COF-p for comparison is shown below: .

[0037] from Fig.10It can be seen that the Nyquist radius of TPPy-PBT-COF-v is significantly smaller than that of TPPy-PBT-COF-p and TPPy-PBT-COF, indicating that TPPy-PBT-COF-v has the smallest electrochemical resistance and the highest charge transfer ability. In addition, the photocurrent response signal shows ( Fig.11 ) TPPy-PBT-COF-v showed a stronger photocurrent response signal than the other two COFs, further proving that TPPy-PBT-COF-v is an excellent and efficient photocatalyst. This shows that the DA-type covalent organic framework provided by the present invention has an asymmetric benzothiadiazole ligand and 1,3,6,8-tetrakis(4-aminophenyl)pyrene as the main structure, and a double π bridge as the connection to construct a D-π-π-A structure. The structural design of the π bridge extension effectively reduces the band gap of the framework material, improves the charge delocalization ability, improves the charge transfer efficiency, and thus improves the high photocatalytic activity.

[0038] Example 3 The DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligand catalyzes the oxidation of thioether to synthesize sulfoxide under visible light.

[0039] Weigh 10 mg TPPy-PBT-COF-v as the catalyst for the photocatalytic reaction, 0.3 mmol anisole substrate (Table 1, 1a-1e), ethanol as the reaction solvent, 10 W blue LED light, 1 bar oxygen atmosphere. Thin layer chromatography (TLC) was used to monitor the reaction progress and determine the reaction time. The product NMR was based on diphenylacetonitrile as the internal standard, and the yield was calculated by 1 The catalytic results are shown in Table 1.

[0040] Table 1 Oxidation of sulfide to sulfoxide catalyzed by TPPy-PBT-COF-v

[0041] The H NMR spectra of the products of photocatalytic oxidation of 1a~1e anisole substrates in Table 1 are as follows: Figures 12 to 16 shown.

[0042] It can be seen from Table 1 that the catalytic oxidation of sulfide to synthesize sulfoxide under the catalysis of D-π-π-A type TPPy-PBT-COF-v can be completed within 6 hours with a yield of more than 90%. This indicates that the DA-type covalent organic framework containing benzothiadiazole units has a great advantage in photocatalytic sulfide by adding a π-bridge conjugated structure.

[0043] Comparative Example 1 The difference from Example 3 is that TPPy-PBT-COF is used as a catalyst to catalyze the oxidation of sulfide to synthesize sulfoxide under visible light. The catalytic results are shown in Table 2.

[0044] Table 2 Oxidation of sulfide to sulfoxide catalyzed by TPPy-PBT-COF

[0045] Comparative Example 2 The difference from Example 3 is that TPPy-PBT-COF-p is used as a catalyst to catalyze the oxidation of sulfide to synthesize sulfoxide under visible light. The catalytic results are shown in Table 3.

[0046] Table 3 Oxidation of sulfide to sulfoxide catalyzed by TPPy-PBT-COF-p

[0047] Comparing Tables 1 to 3, we can see that under the catalysis of D-π-π-A type TPPy-PBT-COF-v, the reaction can be completed within 6 hours with a yield of more than 90%; while TPPy-PBT-COF-p and TPPy-PBT-COF without π-bridge structure have a catalytic efficiency of 11% to 45% in the same time (6 hours), which is significantly lower than TPPy-PBT-COF-v. This shows that adding π-bridge structure can significantly improve the photocatalytic performance of DA-type COF based on benzothiadiazole unit.

[0048] Example 4 To verify the stability and reusability of TPPy-PBT-COF-v, thioanisole 1a was catalyzed to oxidize sulfide to synthesize sulfoxide under visible light, and the specific experimental process was the same as 1a in Example 3. The covalent organic framework was recovered and reused 5 times, and the reaction time and yield of each reaction are shown in Table 4.

[0049] Table 4 Yield of TPPy-PBT-COF-v after 5 times of reuse

[0050] Fig.17 PXRD pattern of TPPy-PBT-COF-v after repeated use for 5 times. Fig.17 It can be seen that TPPy-PBT-COF-v remains stable after being reused 5 times, indicating that it is recyclable and reusable.

[0051] Example 5 The DA-type covalent organic framework TPPy-PBT-COF-v with asymmetric benzothiadiazole ligand catalyzes the oxidation of tetrahydroisoquinoline compounds to synthesize isoquinolone compounds under visible light.

[0052] Weigh 10 mg TPPy-PBT-COF-v as the catalyst for the photocatalytic reaction, 0.3 mmol tetrahydroisoquinoline compounds (Table 5, 2a~2e), ethanol as the reaction solvent, 10 W blue LED light, 1 bar oxygen atmosphere. Thin layer chromatography (TLC) was used to monitor the reaction progress and determine the reaction time. The product NMR was based on diphenylacetonitrile as the internal standard, and the yield was calculated by 1 H NMR spectrum data analysis.

[0053] Table 5 Catalytic oxidation of tetrahydroisoquinoline compounds to synthesize isoquinolone compounds

[0054] The H NMR spectra of the products of the photocatalytic oxidation of tetrahydroisoquinoline compounds 2a~2e in Table 5 are as follows Figures 18 to 22 shown.

[0055] As can be seen from Table 5, D-π-π-A type TPPy-PBT-COF-v photocatalytically oxidizes tetrahydroisoquinoline compounds, which are more difficult to oxidize, to synthesize isoquinolone compounds with a yield of more than 70%.

[0056] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A DA-type covalent organic framework based on an asymmetric benzothiadiazole ligand, characterized in that: The structure represented by formula (I) is used as a structural repeating unit; Formula (I).

2. The asymmetric benzothiadiazole ligand of claim 1 is constructed based on the DA-type covalent organic framework of the asymmetric benzothiadiazole ligand, characterized in that: Its structural formula is shown in formula (II); Formula (II).

3. The method for preparing a DA-type covalent organic framework based on an asymmetric benzothiadiazole ligand according to claim 1, characterized in that: The steps include: The asymmetric benzothiadiazole ligand shown in formula (II) and 1,3,6,8-tetrakis(4-aminophenyl)pyrene are dissolved in an organic solvent, acetic acid is added as a catalyst, and a DA-type covalent organic framework based on the asymmetric benzothiadiazole ligand is synthesized by solvothermal reaction.

4. The preparation method according to claim 3, characterized in that: The molar ratio of the asymmetric benzothiadiazole ligand represented by formula (II) to 1,3,6,8-tetrakis(4-aminophenyl)pyrene is (1.5-3):

1.

5. The preparation method according to claim 3, characterized in that: The organic solvent is a mixed solution of o-dichlorobenzene and anhydrous ethanol; The volume ratio of o-dichlorobenzene and anhydrous ethanol is (2.5~4):

1.

6. The preparation method according to claim 3, characterized in that: The concentration of the asymmetric benzothiadiazole ligand represented by formula (II) in the organic solvent is 0.04-0.08 mol / L.

7. The preparation method according to claim 3, characterized in that: The temperature of the solvothermal reaction is 100~150 ℃; the time of the solvothermal reaction is 60~80 h.

8. Use of the DA type covalent organic framework based on asymmetric benzothiadiazole ligands as claimed in claim 1 or the DA type covalent organic framework based on asymmetric benzothiadiazole ligands prepared by the preparation method as claimed in claim 3 as a photocatalyst.

9. The use according to claim 8, characterized in that The application includes: catalytic oxidation of thioether to synthesize sulfoxide.

10. The use according to claim 8, characterized in that The application includes: catalytic oxidation of tetrahydroisoquinoline compounds to synthesize isoquinolone compounds.

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