Preparation method of an expanded porphyrin (1.0.1.0.1.0) and its dirhodium and trirhodium complexes

Abstract

The present invention belongs to the technical field of organometallic complexes and relates to a preparation method of expanded porphyrin (1.0.1.0.1.0) and its dirhodium and trirhodium complexes. Based on the novel expanded porphyrin (1.0.1.0.1.0), the present invention modifies the ring center (forming metalloporphyrin by substituting the hydrogen on the nitrogen atom at the porphyrin center with metal ions). Using 1-tert-butoxycarbonyl-2-pyrroleboronic acid as a raw material, a coupling reaction is first carried out to synthesize bipyrrole (DPy), and then a condensation reaction is carried out with aromatic aldehyde to generate expanded porphyrin (1.0.1.0.1.0). Finally, based on the obtained expanded porphyrin (1.0.1.0.1.0), its ring center is modified to obtain dirhodium and trirhodium complexes. The synthesis route of the present invention is relatively simple and the yield is high. The obtained compounds are not only used in the field of metal aromaticity research, but also can be used as molecular catalysts for multi-metal photocatalytic / electrocatalytic hydrogen production and photocatalytic / electrocatalytic carbon dioxide reduction, and can be used as new catalysts for high-performance fuel cells and carbon neutralization and carbon cycle.

Description

Technical Field

[0001] The present invention belongs to the technical field of organometallic complexes, relates to expanded porphyrins, and particularly relates to a preparation method of an expanded porphyrin (1.0.1.0.1.0) and its dirhodium and trirhodium complexes. Background Art

[0002] Expanded porphyrins are a class of nitrogen-containing macrocyclic compounds formed by more than four pyrroles, and have unique functions in the fields of catalysis, organic photovoltaics, and anion recognition. Because of such excellent advantages, the inventor utilizes the multidentate ligand ability and macrocyclic structure of expanded porphyrins to prepare dirhodium and trirhodium metal complexes through simple coordination reactions, and realizes the regulation of their infrared spectral properties by adjusting the molecular structures of the dirhodium and trirhodium metal complexes.

[0003] Using bipyrrole as a raw material to undergo a condensation reaction with pentafluorobenzaldehyde to generate an expanded porphyrin (1.0.1.0.1.0), it is found that the expanded porphyrin (1.0.1.0.1.0) has a highly planar molecular structure and strong antiaromatic properties; through a simple coordination reaction, tetracarbonyl dirhodium or tricarbonyl trirhodium is coordinated in the macrocyclic cavity of the expanded porphyrin (1.0.1.0.1.0) to obtain the dirhodium or trirhodium metal complex of the expanded porphyrin (1.0.1.0.1.0). Summary of the Invention

[0004] The purpose of the present invention is to provide a preparation method of an expanded porphyrin (1.0.1.0.1.0).

[0005] Technical Solution

[0006] A preparation method of an expanded porphyrin (1.0.1.0.1.0), the reaction equation of which is

[0007]

[0008] Comprises the following steps:

[0009] A. In a Schlenk tube, add bipyrrole (DPy) and pentafluorobenzaldehyde, displace with argon, add dichloromethane and stir evenly, then continue to add boron trifluoride diethyl ether complex, and stir and react at room temperature in the dark;

[0010] B. Continue to add 2,3-dichloro-5,6-dicyano-p-benzoquinone, and stir and react at room temperature in the dark;

[0011] C. First perform alumina column chromatography on the system, collect the red solution, spin-dry to remove the organic solvent to obtain a crude product, and then perform silica gel column chromatography purification using a mixed solution of dichloromethane and n-hexane as an eluent, and spin-dry to remove the organic solvent to obtain a bright purple solid 24R, which is the expanded porphyrin (1.0.1.0.1.0).

[0012] In a preferred disclosure example of the present invention, in step A, the light-shielded stirring reaction is carried out for 1 to 5 h, preferably 3 h.

[0013] In a preferred disclosure example of the present invention, in step A, the molar and volume ratio of DPy:pentafluorobenzaldehyde:dichloromethane:boron trifluoride diethyl ether complex is 1 to 5 mmol:1 to 5 mmol:50 to 300 ml:0.01 to 0.2 mmol, preferably 3 mmol:3 mmol:150 ml:0.09 mmol.

[0014] In a preferred disclosure example of the present invention, in step B, the molar ratio of 2,3-dichloro-5,6-dicyano-p-benzoquinone to bipyrrole is 0.5 to 3 mmol:0.5 to 5 mmol, preferably 1 mmol:1 mmol.

[0015] In a preferred disclosure example of the present invention, in step C, for the alumina column chromatography, neutral alumina is used as the stationary phase, the diameter of the chromatography column is 2 cm, the column height is 12 cm, the column is loaded with the wet method, and dichloromethane is used as the eluent.

[0016] In a preferred disclosure example of the present invention, in step C, for the silica gel column chromatography, silica gel of 200 to 300 mesh is used as the stationary phase, the diameter of the chromatography column is 1 cm, the column height is 15 cm, the column is loaded with the dry method, and a mixed solvent of dichloromethane and n-hexane with a volume ratio of 1:1 is used as the eluent.

[0017] The second object of the present invention is to disclose a preparation method of an expanded porphyrin (1.0.1.0.1.0) dirhodium complex, and its reaction equation is

[0018]

[0019] It includes the following steps:

[0020] (A) Weigh 24R of expanded porphyrin (1.0.1.0.1.0) and place it in a Schlenk tube, add dichloromethane, sodium acetate and dicarbonylrhodium dichloride dimer, and heat and stir at 35 to 45 °C for 0.5 to 3 h, preferably heat and stir at 40 °C for 2 h;

[0021] (B) Using silica gel as the stationary phase, the diameter of the chromatography column is 2 ml, the column height is 15 ml, the column is loaded with the wet method, and a mixed solvent of n-hexane and dichloromethane is used as the eluent for column chromatography separation and purification to obtain red granular 2Rh, that is, the expanded porphyrin (1.0.1.0.1.0) dirhodium complex.

[0022] In a preferred disclosure example of the present invention, in step (A), the molar and volume ratios of 24R, dichloromethane, sodium acetate, and dirhodium dicarbonyl chloride dimer are 0.01 - 0.05 mmol: 20 - 50 mL: 0.1 - 0.5 mmol: 0.1 - 0.5 mmol, preferably 0.02 mmol: 30 mL: 0.2 mmol: 0.2 mmol.

[0023] In a preferred disclosure example of the present invention, the stationary phase silica gel in step (B) is 200 - 300 mesh; the eluent is a mixture of n - hexane and dichloromethane mixed by a volume ratio of 10:1.

[0024] The third object of the present invention is to disclose a preparation method of an expanded porphyrin (1.0.1.0.1.0) tri - rhodium complex, and its reaction equation is

[0025]

[0026] It includes the following steps:

[0027] (1) Weigh 24R of expanded porphyrin (1.0.1.0.1.0) and place it in a Schlenk tube, add toluene, sodium acetate, and dirhodium dicarbonyl chloride dimer, and heat and stir at 80 - 120 °C for 2 - 12 h, preferably heat and stir at 100 °C for 6 h;

[0028] (2) Using silica gel as the stationary phase, the diameter of the chromatographic column is 2 cm, the column height is 15 cm, load the column by the wet method, and use a mixed solvent of n - hexane and dichloromethane as the eluent for column chromatography separation and purification to obtain purple - black granular 3Rh, that is, the expanded porphyrin (1.0.1.0.1.0) tri - rhodium complex.

[0029] In a preferred disclosure example of the present invention, in step (1), the molar and volume ratios of 24R, toluene, sodium acetate, and dirhodium dicarbonyl chloride dimer are 0.01 - 0.05 mmol: 20 - 50 mL: 0.1 - 0.5 mmol: 0.1 - 0.5 mmol, preferably 0.03 mmol: 30 mL: 0.3 mmol: 0.3 mmol.

[0030] In a preferred disclosure example of the present invention, the stationary phase silica gel in step (2) is 200 - 300 mesh; the eluent is a mixture of n - hexane and dichloromethane mixed by a volume ratio of 10:1.

[0031] Based on the novel expanded porphyrin (1.0.1.0.1.0), the present invention modifies the ring center (forming metal porphyrin by replacing the hydrogen on the nitrogen atom at the center of porphyrin with metal ions). Using 1-tert-butoxycarbonyl-2-pyrroleboronic acid as the raw material, a coupling reaction is first carried out to synthesize bipyrrole (DPy), and then a condensation reaction is carried out with aromatic aldehyde to generate the expanded porphyrin (1.0.1.0.1.0). Finally, based on the obtained expanded porphyrin (1.0.1.0.1.0), its ring center is modified to obtain dirhodium and trirhodium complexes.

[0032] The expanded porphyrin (1.0.1.0.1.0) and its dirhodium and trirhodium complexes prepared by the present invention have the following molecular structures:

[0033]

[0034] The molecular formulas of the three compounds are: 24R: C 45 H 15 F 15 N6, 2Rh: C 49 H 13 F 15 N6O4Rh2, 3Rh: C 48 H 12 F 15 N6O3Rh3.

[0035] Beneficial effects

[0036] The synthetic route of the expanded porphyrin in the present invention is relatively simple, and the synthetic yield is high. The synthesized expanded porphyrin (1.0.1.0.1.0) and its dirhodium and trirhodium complexes have simple steps, convenient operation and good yields. The prepared compounds are not only used in the field of metal aromaticity research, but also can be used as molecular catalysts for multi-metal photocatalytic / electrocatalytic hydrogen production and photocatalytic / electrocatalytic carbon dioxide reduction, and can be used as new catalysts for high-performance fuel cells and carbon neutrality and carbon cycle. Description of the drawings

[0037] Figure 1 . High-resolution mass spectrum of the target product 24R;

[0038] Figure 2 . High-resolution mass spectrum of the target product 2Rh;

[0039] Figure 3 . High-resolution mass spectrum of the target product 3Rh;

[0040] Figure 4 . 1H NMR spectrum of the target product 2Rh in CDCl3 1 H NMR spectrum;

[0041] Figure 5 . 1H NMR spectrum of the target product 3Rh in CDCl31 1H NMR spectrum

[0042] Figure 6 . Infrared absorption spectra of the target products 2Rh and 3Rh Detailed implementation manners

[0043] The present invention will be described in detail below in conjunction with embodiments, so that those skilled in the art can better understand the present invention, but the present invention is not limited to the following embodiments

[0044] Example 1

[0045] A preparation method of an expanded porphyrin (1.0.1.0.1.0), and its reaction equation is

[0046]

[0047] It includes the following steps

[0048] A. In a Schlenk tube, add dipyrrole (DPy) and pentafluorobenzaldehyde, displace with argon, add dichloromethane and stir evenly, then continue to add boron trifluoride diethyl ether complex, and stir and react at room temperature in the dark for 3 h. Among them, the molar and volume ratio of DPy:pentafluorobenzaldehyde:dichloromethane:boron trifluoride diethyl ether complex is 3 mmol:3 mmol:150 ml:0.09 mmol

[0049] B. Continue to add 2,3-dichloro-5,6-dicyano-p-benzoquinone, and stir and react at room temperature in the dark for 1 h. Among them, the molar ratio of 2,3-dichloro-5,6-dicyano-p-benzoquinone to dipyrrole is 1 mmol:1 mmol

[0050] C. First perform alumina column chromatography on the system, collect the red solution, spin-dry to remove the organic solvent to obtain the crude product, and then perform silica gel column chromatography purification with a mixed solution of dichloromethane and n-hexane as the eluent. After spin-drying to remove the organic solvent, a bright purple solid 24R, that is, expanded porphyrin (1.0.1.0.1.0), is obtained. Among them, for the alumina column chromatography, neutral alumina is used as the stationary phase, the diameter of the chromatographic column is 2 cm, the column height is 12 cm, wet packing is used, and dichloromethane is used as the eluent; for the silica gel column chromatography, silica gel of 200-300 mesh is used as the stationary phase, the diameter of the chromatographic column is 1 cm, the column height is 15 cm, dry packing is used, and a mixed solution of dichloromethane and n-hexane with a volume ratio of 1:1 is used as the eluent

[0051] The yield of the product expanded porphyrin (1.0.1.0.1.0) is 9%

[0052] From Figure 1The HR-MALDI-TOF mass spectrum of Compound 24R shows that the measured value of the target product 24R is 924.1117, and its theoretical value is 924.1113, indicating that the measured value is consistent with the theoretical value and that Compound 24R has been successfully prepared.

[0053] Example 2

[0054] A method for preparing an expanded porphyrin (1.0.1.0.1.0) dirhodium complex, the reaction equation of which is

[0055]

[0056] Comprising the following steps:

[0057] (A) Weigh 24R of expanded porphyrin (1.0.1.0.1.0) and place it in a Schlenk tube. Add dichloromethane, sodium acetate, and dirhodium dicarbonyl chloride dimer, and heat and stir at 40 °C for 2 h. Among them, the molar and volume ratios of 24R, dichloromethane, sodium acetate, and dirhodium dicarbonyl chloride dimer are 0.02 mmol: 30 mL: 0.2 mmol: 0.2 mmol;

[0058] (B) Using silica gel as the stationary phase, the diameter of the chromatographic column is 2 ml, and the column height is 15 ml. Load the column by the wet method, and use a mixed solvent of n-hexane and dichloromethane as the eluent for column chromatography separation and purification to obtain red granular 2Rh, that is, the expanded porphyrin (1.0.1.0.1.0) dirhodium complex. The stationary phase silica gel is 200 - 300 mesh; the eluent is a mixture of n-hexane and dichloromethane in a volume ratio of 10:1. The yield of the product expanded porphyrin (1.0.1.0.1.0) dirhodium complex is 92%.

[0059] From Figure 2 The HR-MALDI-TOF mass spectrum of Compound 2Rh, it can be seen that the measured value of the target product 2Rh is 1239.8867, and its theoretical value is 1239.8863, indicating that the measured value is consistent with the theoretical value and that Compound 2Rh has been successfully prepared. Attached Figure 4 .2Rh's 1 1H NMR spectrum shows that the broad peak of 2Rh at about δ = 33.98 ppm belongs to the uncoordinated in-ring NH, and the multiplet in the range from δ 3.15 to 2.42 ppm is the out-of-ring hydrogen of pyrrole, indicating that Compound 2Rh has been successfully prepared.

[0060] Example 3

[0061] A method for preparing an expanded porphyrin (1.0.1.0.1.0) trirhodium complex, the reaction equation of which is

[0062]

[0063] It includes the following steps:

[0064] (1) Weigh 24R of expanded porphyrin (1.0.1.0.1.0) and place it in a Schlenk tube. Add toluene, sodium acetate, and rhodium dicarbonyl chloride dimer, and heat and stir at 100 °C for 6 h. Among them, the molar and volume ratios of the 24R, toluene, sodium acetate, and rhodium dicarbonyl chloride dimer are 0.03 mmol: 30 mL: 0.3 mmol: 0.3 mmol;

[0065] (2) Using silica gel as the stationary phase, the diameter of the chromatographic column is 2 cm, and the column height is 15 cm. Load the column by the wet method, and use a mixed solvent of n-hexane and dichloromethane as the eluent for column chromatography separation and purification to obtain purple-black granular 3Rh, that is, the trirhodium complex of expanded porphyrin (1.0.1.0.1.0). Among them, the stationary phase silica gel is 200 - 300 mesh; the eluent is a mixture of n-hexane and dichloromethane in a volume ratio of 10:1.

[0066] The yield of the product, the trirhodium complex of expanded porphyrin (1.0.1.0.1.0), is 45%.

[0067] From Figure 3 In the HR-MALDI-TOF mass spectrum of compound 3Rh, it can be seen that the measured value of the target product 2Rh is 1313.7894, and its theoretical value is 1313.7891, indicating that the measured value is consistent with the theoretical value, indicating that compound 3Rh has been successfully prepared.

[0068] Figure 5 of 3Rh 1 In the 1H NMR spectrum of 3Rh, it can be seen that the two groups of peaks of 3Rh in the range of δ = -3.55 and -4.33 ppm are the out-of-ring hydrogens of pyrrole, indicating that compound 3Rh has been successfully prepared.

[0069] Figure 6 Infrared spectra of the dirhodium and trirhodium complexes of expanded porphyrin (1.0.1.0.1.0). The synthesized dirhodium and trirhodium complexes of expanded porphyrin (1.0.1.0.1.0), 2Rh and 3Rh, were studied for their infrared spectral properties by potassium bromide pellet pressing. Different from common carbonyl complexes, the infrared spectra of the two rhodium complexes showed their unique infrared absorption in the range of 2100 cm -1 to 1800 cm -1 range, indicating that compounds 2Rh and 3Rh have been successfully prepared and have unique molecular structures and optoelectronic structures.

[0070] The above are only embodiments of the present invention, and do not thus limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made by using the description of the present invention, or direct or indirect application in other related technical fields, shall similarly be included within the patent protection scope of the present invention.

Claims

1. A method for preparing an expanded porphyrin (1.0.1.0.1.0) dirhodium complex, characterized in that, The reaction equation is ， It includes the following steps: (A)Weigh 24R of expanded porphyrin (1.0.1.0.1.0) and place it in a Schlenk tube. Add dichloromethane, sodium acetate, and rhodium dicarbonyl chloride dimer, and heat and stir at 35 - 45 °C for 0.5 - 3 h. Among them, the molar and volume ratios of 24R, dichloromethane, sodium acetate, and rhodium dicarbonyl chloride dimer are 0.01 - 0.05 mmol: 20 - 50 mL: 0.1 - 0.5 mmol: 0.1 - 0.5 mmol; (B)Using silica gel as the stationary phase, the diameter of the chromatographic column is 2 ml, and the column height is 15 ml. Load the column by the wet method, and use a mixed solvent of n - hexane and dichloromethane as the eluent for column chromatography separation and purification to obtain red granular 2Rh, that is, the bis - rhodium complex of expanded porphyrin (1.0.1.0.1.0).

2. The preparation method of the dirhodium complex of expanded porphyrin (1.0.1.0.1.0) according to claim 1, characterized in that: In step (A), weigh 24R of expanded porphyrin (1.0.1.0.1.0) and place it in a Schlenk tube. Add dichloromethane, sodium acetate, and rhodium dicarbonyl chloride dimer, and heat and stir at 40 °C for 2 h.

3. The preparation method of the dirhodium complex of expanded porphyrin (1.0.1.0.1.0) according to claim 1, characterized in that: In step (A), the molar and volume ratios of 24R, dichloromethane, sodium acetate, and rhodium dicarbonyl chloride dimer are 0.02 mmol: 30 mL: 0.2 mmol: 0.2 mmol.

4. The method for preparing a dirhodium complex of expanded porphyrin (1.0.1.0.1.0) according to claim 1, characterized in that: The stationary - phase silica gel in step (B) is 200 - 300 mesh.

5. The preparation method of the dirhodium complex of expanded porphyrin (1.0.1.0.1.0) according to claim 1, characterized in that: The eluent in step (B) is a mixture of n - hexane and dichloromethane in a volume ratio of 10:

1.

6. A method for preparing an expanded porphyrin (1.0.1.0.1.0) trirhodium complex, characterized in that, The reaction equation is ， It includes the following steps: (1)Weigh 24R of expanded porphyrin (1.0.1.0.1.0) and place it in a Schlenk tube. Add toluene, sodium acetate, and rhodium dicarbonyl chloride dimer, and heat and stir at 80 - 120 °C for 2 - 12 h. Among them, the molar and volume ratios of 24R, toluene, sodium acetate, and rhodium dicarbonyl chloride dimer are 0.01 - 0.05 mmol: 20 - 50 mL: 0.1 - 0.5 mmol: 0.1 - 0.5 mmol; (2)Using silica gel as the stationary phase, the diameter of the chromatographic column is 2 cm, and the column height is 15 cm. Load the column by the wet method, and use a mixed solvent of n - hexane and dichloromethane as the eluent for column chromatography separation and purification to obtain purple - black granular 3Rh, that is, the tris - rhodium complex of expanded porphyrin (1.0.1.0.1.0).

7. The preparation method of the expanded porphyrin (1.0.1.0.1.0) trirhodium complex according to claim 6, characterized in that: In step (1), weigh 24R of expanded porphyrin (1.0.1.0.1.0) and place it in a Schlenk tube. Add toluene, sodium acetate, and rhodium dicarbonyl chloride dimer, and heat and stir at 100 °C for 6 h.

8. The preparation method of the expanded porphyrin (1.0.1.0.1.0) tri-rhodium complex according to claim 6, characterized in that: In step (1), the molar and volume ratios of 24R, toluene, sodium acetate, and rhodium dicarbonyl chloride dimer are 0.03 mmol: 30 mL: 0.3 mmol: 0.3 mmol.

9. The preparation method of the expanded porphyrin (1.0.1.0.1.0) trirhodium complex according to claim 6, characterized in that: The stationary - phase silica gel in step (2) is 200 - 300 mesh.

10. The preparation method of the expanded porphyrin (1.0.1.0.1.0) trirhodium complex according to claim 6, characterized in that: The eluent in step (2) is a mixture of n - hexane and dichloromethane in a volume ratio of 10:1.

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