A metalloporphyrin-pyrrolodiketone conjugate compound, and a preparation method and application thereof

Abstract

The application discloses a metal porphyrin-pyrrolopyrrolidone conjugated compound and a preparation method and application thereof. The compound has the structure shown in the following formula I or formula II: wherein R1 is selected from * represents a connecting position of a carbon-carbon triple bond; represents an aromatic group; R represents an alkyl group; and M represents a heavy metal atom. In the compound structure, the construction of an electron donor-acceptor conjugated system and the introduction of the heavy metal atom can effectively promote intramolecular charge transfer absorption, and due to the heavy metal atom effect, a singlet excited state is converted into a long-lifetime triplet excited state through intersystem crossing, effective triplet excited state absorption is generated, and then the compound has high-performance nonlinear optical material.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of nonlinear optical materials. More particularly, it relates to a metalloporphyrin-pyrromethene conjugated compound and its preparation method and application. BACKGROUND

[0002] Since the birth of laser, laser has been gradually applied to various fields. At the same time, in order to deal with the blindness and damage to optical sensors and human eyes caused by laser, the research and development of laser protection materials have been highly valued. Among them, the optical limiting material based on nonlinear optical effect has the characteristics of "high resistance low pass", that is, under lower intensity laser, the transmittance of the material to the laser does not change with the increase of the intensity of the incident laser, showing linear transmittance, while under high intensity laser, the transmittance of the material to the laser decreases with the increase of the intensity of the incident laser, showing nonlinear transmittance. Therefore, the optical limiting material based on nonlinear optical effect can attenuate high intensity laser without affecting the information reception of optical sensors and human eyes, thereby protecting human eyes and sensitive optical instruments from laser damage. In recent years, the research on optical limiting material based on nonlinear optical effect has attracted widespread attention.

[0003] The research on optical limiting material started from inorganic crystals, whose nonlinear effect originates from resonance absorption and lattice distortion. It has the advantages of good stability, simple structure, easy processing and long service life. However, it has the disadvantages of narrow protection waveband and low damage threshold, so it is not good at protecting the tunable laser with wide waveband. Organic optical limiting material is due to the nonlinear polarization of the delocalized π-electrons in the material under the action of external optical field. Compared with inorganic materials, organic materials can be designed at the molecular level according to the needs, and unlike inorganic materials, nonlinear absorption can be generated in the non-resonant region. Among many promising materials, highly delocalized π-electron conjugated porphyrin-based materials show high optical limiting performance. And because of its easy modification and derivation, easy performance control, high nonlinear coefficient and fast response speed, it is considered to be a good candidate material with strong optical limiting response. However, due to the strong π-π stacking of porphyrin compounds, the solubility of the prepared optical limiting material is poor, and the intrinsic absorption wavelength range of porphyrin is narrow, which limits its practical application in laser protection. SUMMARY

[0004] Based on the above facts, the purpose of the present application is to provide a metalloporphyrin-pyrromethene conjugated compound and its preparation method and application.

[0005] To achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0006] In one aspect, the present application provides a metalloporphyrin-pyrrolodiketone conjugated compound, which has the following structure of formula I or formula II:

[0007]

[0008] wherein R1 is selected from * indicates the connection site with the carbon-carbon triple bond; indicates an aromatic group;

[0009] R represents an alkyl group;

[0010] M represents a heavy metal atom.

[0011] That is, the structural formula of the compound is:

[0012]

[0013]

[0014] In the technical scheme of the present application, through the construction of an electron donor-acceptor conjugated system and the introduction of a heavy metal atom, the intramolecular charge transfer absorption can be effectively promoted, and due to the heavy metal atom effect, the singlet excited state is converted into a long-lived triplet excited state through intersystem crossing, thereby producing effective triplet excited state absorption, and the compound has high-performance nonlinear optical material. At the same time, compared with conventional porphyrin compounds, the compound has higher solubility and can be better used in actual laser protection.

[0015] Specifically, in the structure of the compound, the structural characteristics of the porphyrin derivative are utilized, and the pyrrolodiketone derivative with strong electron-withdrawing properties is connected through a covalent bond (carbon-carbon triple bond) to form an organic conjugated molecule with a large π-electron conjugated system, strong intramolecular charge transfer absorption, and heavy metal atom effect fusion. The porphyrin-pyrrolodiketone conjugated structure provided in the technical scheme of the present application is based on its large conjugated structure and strong donor-acceptor interaction, and the material exhibits excellent intramolecular charge transfer absorption; the introduction of a heavy metal atom in the porphyrin skeleton of the material causes spin-orbit coupling due to the heavy atom effect, which causes the singlet excited state of the material to undergo intersystem crossing to form a triplet excited state, further improving the absorption of the excited state of the material, thereby obtaining high-performance nonlinear optical properties and realizing application in laser limiting.

[0016] Further, R1 is selected from any one of * indicates the connection site with the carbon-carbon triple bond.

[0017] Further, the alkyl group is selected from a linear alkyl group or a branched alkyl group.

[0018] Further, the linear alkyl group is a C1-C12 linear alkyl group. Exemplary linear alkyl groups are C6-C12 branched alkyl groups, including but not limited to one selected from the group consisting of -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)9CH3, -(CH2) 10 CH3or -(CH2) 11 CH3.

[0019] Further, the branched alkyl group has a structural formula of wherein x, n and m are each independently selected from positive integers from 1 to 12. Exemplary branched alkyl groups include but are not limited to one selected from the group consisting of CH3.

[0020] Further, the heavy metal atom is selected from one of Zn, Mg, Pd and Cu.

[0021] In one aspect, the present application provides a method for preparing the metalloporphyrin-pyrrolodiketone conjugate compound as described above, comprising the following steps:

[0022] a compound represented by Formula I-1 or Formula II-1

[0023]

[0024] a trimethylsilane removal reaction is performed to obtain a compound represented by Formula I-2 or II-2

[0025]

[0026] a compound represented by Formula I-2 or II-2 is reacted with a compound represented by Formula III

[0027]

[0028] a sonogashira coupling reaction is performed, and the resulting product is separated and purified to obtain the metalloporphyrin-pyrrolodiketone conjugate compound;

[0029] wherein R' is selected from -Br or -I;

[0030] the M and R are defined as defined above.

[0031] Further, the trimethylsilane removal reaction has a route as shown in the following formula:

[0032]

[0033] Further, the de-trimethylsilane reaction comprises the following steps: reacting the compound shown as formula I-1 or formula II-1 with TBAF at room temperature to remove the TMS protecting group to obtain the compound shown as formula I-2 or formula II-2.

[0034] Further, the reaction time at room temperature is 0.5-4h.

[0035] Further, the

[0036] Further, the molar ratio of the compound shown as formula I-1 to TBAF is 1:4.1-1:5.

[0037] Further, the molar ratio of the compound shown as formula II-1 to TBAF is 1:2.1-1:3.

[0038] Further, the molar ratio of the compound shown as formula I-2 to the compound shown as formula III is 1:4.1-1:5.

[0039] Further, the molar ratio of the compound shown as formula II-2 to the compound shown as formula IV is 1:2.1-1:3.

[0040] Further, the route of the sonogashira coupling reaction is shown as follows:

[0041]

[0042]

[0043] Further, the preparation of the sonogashira coupling reaction comprises the following steps:

[0044] The compound shown as formula I-2 or formula II-2, the compound shown as formula III, and a catalyst are placed in a Schlenk tube, a solvent, and a basic substance are added;

[0045] The obtained solution is replaced with nitrogen during the freeze-thaw cycle, and is placed in an oil bath for heating and stirring for 24-48h;

[0046] The reaction is stopped and returned to room temperature, the reaction solution is poured into methanol and stirred for 1-3h, and then the solid is extracted by suction filtration;

[0047] The solid is purified by a Soxhlet extractor, and the catalyst, reactant, and by-product are removed by methanol and n-hexane in sequence;

[0048] The product is extracted by dichloromethane and then added to methanol for settling, and the solid extracted by suction filtration is vacuum dried at 40-60℃ for 24-48h.

[0049] Further, the catalyst is selected from one or more of tris(dibenzylideneacetone)dipalladium, triphenylphosphine and cuprous iodide.

[0050] Further, the basic condition is triethylamine or diisopropylamine.

[0051] Further, the solvent is selected from one of toluene, xylene and tetrahydrofuran.

[0052] Further, the temperature of the sonogashira coupling reaction is 80-100℃ and the time is 24-48h.

[0053] Further, the preparation route of the compound shown in formula I-1 is as shown in the following formula:

[0054]

[0055] Further, the M y+ , M is selected from one of Zn, Mg, Pd and Cu, and y is 2 or 3.

[0056] Further, the molar ratio of I`-1 to M y+ is 1:3-1:20.

[0057] Further, the preparation of the compound shown in formula I-1 comprises the following steps:

[0058] reacting the pyrrole and 3-trimethylsilylpropynal to obtain a porphyrin derivative;

[0059] further metalizing the porphyrin derivative to obtain the compound shown in formula I-1.

[0060] Further, the molar ratio of the pyrrole to 3-trimethylsilylpropynal is 1:1-1:1.1.

[0061] Further, the temperature of the reaction of the pyrrole and 3-trimethylsilylpropynal is -90~-70℃ and the time is 12-24h.

[0062] Further, the preparation of the compound shown in formula I-1 comprises the following steps:

[0063] dissolving 3-trimethylsilylpropynal in dichloromethane, purging nitrogen to exhaust, and then adding pyrrole dropwise under stirring to mix uniformly;

[0064] after cooling the system to the reaction temperature, adding boron trifluoride ether dropwise, and then recovering to room temperature to continue the reaction overnight after reacting for four hours;

[0065] After 30 minutes, the DDQ was added, and after 30 minutes, the mixture was filtered through a short silica gel column. After removing the solvent, the solid was precipitated using dichloromethane / methanol to obtain the intermediate product I'-1.

[0066] The I'-1 was mixed with the M y+ After replacing the inert gas atmosphere in a flask, a mixed solvent of methanol and water was added, and the reaction was carried out under reflux by stirring in an oil bath for 4-12 hours. After cooling to room temperature, the mixture was filtered through a short silica gel column. After removing the solvent, the solid I-1 was precipitated using dichloromethane / methanol.

[0067] Further, the molar ratio of the pyrrole, 3-trimethylsilylpropynal, and boron trifluoride etherate was 1:1:0.05-1:1.1:0.2.

[0068] Further, the preparation route of the compound represented by Formula II-1 is as follows:

[0069]

[0070] Further, the molar ratio of the II'-1 and the M y+ was 1:3-1:20.

[0071] Further, the preparation of the compound represented by Formula II-1 included the following steps:

[0072] The 2,2'-dipyrrylmethane and 3-trimethylsilylpropynal were reacted to obtain a porphyrin derivative.

[0073] The porphyrin derivative was further metallized to obtain the compound represented by Formula II-1.

[0074] Further, the molar ratio of the 2,2'-dipyrrylmethane and 3-trimethylsilylpropynal was 1:1-1:1.1.

[0075] Further, the reaction temperature of the 2,2'-dipyrrylmethane and 3-trimethylsilylpropynal was 10-30°C, and the reaction time was 12-24 hours.

[0076] Further, the preparation of the compound represented by Formula II-1 included the following steps:

[0077] The 3-trimethylsilylpropynal and 2,2'-dipyrrylmethane were dissolved in dichloromethane, and after exhausting the nitrogen gas, boron trifluoride etherate was added dropwise at room temperature, and the reaction was carried out overnight.

[0078] After 30 minutes, the DDQ was added, and after 30 minutes, the mixture was filtered through a short silica gel column. After removing the solvent, the solid was precipitated using dichloromethane / methanol to obtain the intermediate product I'-1.

[0079] The II'-1 was mixed with the My+ After the inert gas atmosphere is replaced, the mixed solvent of methanol and water is added into the flask, and the reaction is carried out under reflux for 4-12 h in an oil bath with stirring; after being cooled to room temperature, the solid II-1 is obtained by filtering through a short silica gel column and then precipitating from dichloromethane / methanol.

[0080] Further, the molar ratio of the 2,2'-dipyrrolylmethane, 3-trimethylsilylpropynal and boron trifluoride ether is 1:1:0.05-1:1.1:0.2.

[0081] In another aspect, the present application provides a nonlinear optical material prepared from the metalloporphyrin-pyrromethene conjugated compound as described above.

[0082] In another aspect, the present application provides the use of the nonlinear optical material as described above in laser limiting.

[0083] Further, in the use, the laser used is a pulse laser; the pulse width of the pulse laser is 4-8 ns, the pulse frequency is 10 Hz, and the wavelength is 532 nm.

[0084] The beneficial effects of the present application are as follows:

[0085] The metalloporphyrin-pyrromethene conjugated compound provided in the present application has nonlinear optical properties and can be used as a nonlinear optical material. In the structure, the porphyrin structure and the pyrromethene structure are linked by a carbon-carbon triple bond, which not only has a large conjugated π electron and a strong donor-acceptor structure to promote intramolecular charge transfer, but also has a heavy metal atom effect, and the three produce a synergistic effect, so that the material has a large third-order nonlinear coefficient, has excellent intramolecular charge transfer absorption and excited state absorption, and exhibits high nonlinear optical limiting performance, which has important applications in laser protection. The preparation method of the conjugated molecule of the porphyrin-pyrromethene conjugated structure provided in the present application is simple, and the material structure is easy to modify. BRIEF DESCRIPTION OF DRAWINGS

[0086] The specific embodiments of the present application will be further described in detail below with reference to the accompanying drawings.

[0087] Figure 1 The ultraviolet-visible spectrum of the nonlinear optical material PZn-4DPP prepared in Example 1 is shown.

[0088] Figure 2 The nonlinear optical performance diagram of the nonlinear optical material PZn-4DPP prepared in Example 1 is shown.

[0089] Figure 3 The nonlinear optical performance diagram of the nonlinear optical material PZn-4Th prepared in Comparative Example 1 is shown. DETAILED DESCRIPTION

[0090] In order to more clearly illustrate the present application, the present application will be further described with additional specific examples and accompanying drawings. Like reference numerals denote like elements throughout the accompanying drawings. It should be understood that the following description is illustrative only and is not intended to be limiting on the scope of the present application.

[0091] Example 1

[0092] The structural formula of the organic compound based on the metalloporphyrin- pyrrolodipyrrin conjugated structure of the present embodiment is as follows:

[0093]

[0094] The synthesis route of the metalloporphyrin-pyrrolodipyrrin conjugated structure organic compound PZn-4DPP is as follows:

[0095]

[0096] The synthesis of the metalloporphyrin-pyrrolodipyrrin conjugated structure organic compound PZn-4DPP is as follows:

[0097] Synthesis of P-4TMS: 500 ml of dichloromethane was added to a three-necked flask and purged with nitrogen for 15 minutes and cooled to -78°C. 3-Trimethylsilylpropynal (1.35 ml, 9.4 mmol) and pyrrole (0.65 ml, 0.93 mmol) were added in turn under a nitrogen atmosphere and stirred for 15 minutes, then trifluoroboron ether (0.18 ml, 1.47 mmol) was added dropwise. After 4 h of reaction, the reaction was gradually returned to room temperature and reacted overnight. After 2 h of reaction with 2,3-dichloro-5,6-dicyano-p-benzoquinone (1.95 g, 8.6 mmol), it was filtered twice through a short silica gel column, and after removing the solvent, it was precipitated with dichloromethane / methanol to obtain a purple solid P-4TMS (0.35 g, yield 23.2%). 1 H NMR (400 MHz, CDC13): δ = 9.50 (8H, s), 0.63 (36H, s), -1.99 (2H, s).

[0098] Synthesis of PZn-4TMS: P-4TMS (0.137 g, 0.197 mmol) and zinc acetate dihydrate (0.41 g, 1.87 mmol) were added to a 50 ml two-necked flask, 3 ml of methanol and 27 ml of dichloromethane were added under a nitrogen atmosphere, and heated to 75°C to reflux for 1 day. After filtering through a short silica gel column, the solvent was removed, and precipitated with dichloromethane / methanol to obtain a deep purple solid PZn-4TMS (0.146 g, yield 98%). 1H NMR (400 MHz, CDC13): δ = 9.57 (8H, s), 0.63 (36H, s).

[0099] Synthesis of PZn-d-4TMS: PZn-4TMS (0.34 g, 0.45 mmol) was dissolved in 20 ml of tetrahydrofuran, 1 M TBAF in tetrahydrofuran (2 ml, 2 mmol TBAF) was added dropwise at room temperature and stirred for 3 h. After removing the solvent, the dark purple solid was precipitated with dichloromethane / methanol, and then the solid was washed with water, methanol three times, and dried under vacuum to give the purple solid PZn-d-4TMS (93 mg, yield 45%). 1 H NMR (400 MHz, C5D5N): δ = 9.91 (8H, s), 5.25 (4H, s).

[0100] Synthesis of PZn-4DPP: PZn-4DPP (20 mg, 0.043 mmol), BrDPP-1 (102.0 mg, 0.1423 mmol), tris(dibenzylideneacetone)dipalladium (7.9 mg, 4.7 μmol), triphenylphosphine (2.5 mg, 9.5 μmol), cuprous iodide (1.8 mg, 9.5 μmol) were placed in a Schlenk tube under nitrogen atmosphere, and evacuated toluene (15 mL) and diisopropylamine (2 mL) were added. Stirring was performed at 90 °C oil bath for 1 day. After cooling to room temperature, the solid was precipitated by adding to 100 ml of methanol. The solid was purified by a Soxhlet extractor, and the catalyst, reactants and byproducts were removed with methanol and n-hexane in turn. The product was extracted with dichloromethane, and the solid PZn-4DPP (56 mg, yield 43%) was precipitated with dichloromethane / methanol after removing the solvent. 1 HNMR (400 MHz, pyridine-d5): δ = 9.61 (4H, d), 9.32 (4H, d), 9.12 (8H, m), 8.11 (4H, d), 7.65 (4H, dd), 7.07 (4H, dd), 3.98 (16H, t), 2.05 (16H, m), 1.89-1.82 (16H, m), 1.61-1.57 (16H, m), 1.45-1.08 (128H, m) 0.63-0.55 (24H, m). Infrared spectrum: IR (KBr, cm -1 ) 3436, 2910, 2845, 2365, 2160, 1663, 1558, 1400, 1253, 1212, 1090, 1054, 1013, 850, 803, 705. Ultraviolet absorption spectrum as Figure 1 shown, the compound exhibits a wide intramolecular charge transfer absorption band.

[0101] The nonlinear optical properties of the metalloporphyrin-pyrrolopyrrolidone conjugated structure organic compound PZn-4DPP:

[0102] PZn-4DPP was dissolved in 1,1,2,2-tetrachloroethane, loaded into a 1mm quartz cuvette, and its linear transmittance at a wavelength of 532nm was adjusted to 70%. The nonlinear optical properties of the material were tested by Z-scan technology. The test laser was a Nd:YAG pulse laser with a pulse width of 4ns, a pulse frequency of 10Hz, and a laser wavelength of 532nm. The laser incident energy was 20μJ. As shown in Figure 2 the material is a typical anti-saturation absorption nonlinear optical property, the normalized transmittance is reduced to 0.69, so the metalloporphyrin-pyrrolopyrrolidone conjugated structure organic compound PZn-4DPP has a laser limiting effect and can be used for laser protection.

[0103] Example 2

[0104] The structural formula of the metalloporphyrin-pyrrolopyrrolidone conjugated structure organic compound of this example is as follows:

[0105]

[0106] The synthesis route of the organic compound PZn-2DPP is as follows:

[0107]

[0108] The preparation method is as follows

[0109] Synthesis of P-2TMS: 2,2'-dipyrromethane (1.21g, 8.30mmol) and 3-trimethylsilylpropynal (1.05g, 8.30mmol) were dissolved in 2L of deoxygenated dichloromethane, and boron trifluoride ether (0.33ml, 2.63mmol) was added at room temperature. After the reaction overnight, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (2.84g, 12.5mmol) was added to the system and stirred for 40 minutes, and finally triethylamine (5.4ml, 40mmol) was added. After removing the solvent, recrystallization was performed with dichloromethane / methanol, and after suction filtration, purple solid PZn-2TMS (0.26g, yield 12.46%) was obtained, 1 H NMR (400MHz, CDCl3): δ = 10.14 (2H, s), 9.71 (4H, d), 9.32 (4H, d), 0.00 (18H, s), -2.65 (2H, s).

[0110] Synthesis of PZn-2TMS: P-2TMS (0.15 g, 0.3 mmol) and zinc acetate dihydrate (0.66 g, 3 mmol) were dissolved in a mixture solvent of dichloromethane:methanol = 9:1 under nitrogen atmosphere, and heated at 65 °C oil bath for 5 h. After filtration through a short silica gel column, the solvent was removed, and PZn-2TMS (150 mg, yield 88%) was obtained by recrystallization from dichloromethane / methanol. 1 H NMR (400 MHz, CDC13): δ = 10.06 (2H, s), 9.77 (4H, d), 9.30 (4H, d), 0.62 (18H, m).

[0111] Synthesis of PZn-d-2TMS: PZn-2TMS (0.1 g, 0.18 mmol) was dissolved in 20 ml of tetrahydrofuran, and 1 M TBAF in tetrahydrofuran (0.54 ml, 0.54 mmol TBAF) was added dropwise at room temperature for 3 h. After removal of the solvent, the solid was recrystallized from dichloromethane / methanol, and then washed with water, methanol three times, and dried under vacuum to obtain a dark purple solid PZn-d-2TMS (40 mg, yield 53%). 1 H NMR (400 MHz, C5D5N): δ = 10.33 (2H, s), 10.07 (4H, d), 9.54 (4H, d), 5.22 (2H, s).

[0112] Synthesis of PZn-2DPP: PZn-d-2TMS (56 mg, 0.13 mmol), BrDPP-2 (275 mg, 0.29 mmol), tris(dibenzylideneacetone)dipalladium (12 mg, 13 μmol), triphenylphosphine (7 mg, 26 μmol), cuprous iodide (5 mg, 26 μmol) were placed in a Schlenk tube under nitrogen atmosphere, and evacuated toluene (10 mL) and diisopropylamine (2 mL) were added, and stirred at 90 °C oil bath for 1 day. After cooling to room temperature, the solvent was removed, and PZn-2DPP (63 g, 42%) was obtained by column chromatography with dichloromethane / petroleum ether / pyridine (v / v, 2:1:0.03). 1 H NMR (400 MHz, pyridine-d5): δ = 9.65 (4H, d), 9.45 (2H, d), 9.21 (4H, m), 8.14 (2H, d), 7.69 (2H, dd), 7.08 (2H, dd), 3.97 (8H, t), 2.05 (8H, m), 1.91-1.83 (8H, m), 1.61-1.56 (8H, m), 1.43-1.12 (64H, m) 0.63-0.58 (12H, m). Infrared spectroscopy characterization: IR (KBr, cm -1)3430, 2915, 2845, 2365, 2172, 1675, 1546, 1458, 1405, 1265, 1083, 1054, 1025, 849, 803, 715. The UV absorption spectrum is similar to that of Example 1, showing a wide intramolecular charge transfer absorption band.

[0113] The nonlinear optical properties of the metalloporphyrin- diketopyrrolopyrrole conjugated structure organic compound PMg-4DPP:

[0114] PZn-2DPP was dissolved in 1,1,2,2-tetrachloroethane, loaded into a 1mm quartz cuvette, and its linear transmittance at a wavelength of 532nm was adjusted to 70%. The nonlinear optical properties of the material were tested by Z-scan technology. The test laser was a Nd:YAG pulse laser with a pulse width of 4ns, a pulse frequency of 10Hz, and a laser wavelength of 532nm. The laser incident energy was 20μJ. The material has a similar reverse saturation absorption nonlinear optical property to that of Example 1, with a normalized transmittance of 0.73, so the metalloporphyrin- diketopyrrolopyrrole conjugated structure organic compound PZn-2DPP has a laser limiting effect and can be used for laser protection.

[0115] Example 3

[0116] The structural formula of the metalloporphyrin- diketopyrrolopyrrole conjugated structure organic compound of this example is as follows:

[0117]

[0118] The synthesis route of the metalloporphyrin- diketopyrrolopyrrole conjugated structure organic compound PMg-4DPP is similar to that of Example 1, except that all the Zn in the porphyrin structure in the synthesis route is replaced by Mg. The specific synthesis route is as follows:

[0119]

[0120] Compound nuclear magnetic resonance 1 The H NMR and infrared characterization results are similar to those of Example 1, and the UV absorption spectrum is similar to that of Example 1, showing a wide intramolecular charge transfer absorption band.

[0121] The nonlinear optical properties of the metalloporphyrin- diketopyrrolopyrrole conjugated structure organic compound PMg-4DPP:

[0122] PMg-4DPP was dissolved in 1,1,2,2-tetrachloroethane, loaded into a 1 mm quartz cuvette, and its linear transmittance at a wavelength of 532 nm was adjusted to 70%. The nonlinear optical properties of the material were tested by Z-scan technology. The test laser was a Nd:YAG pulse laser, the pulse width was 4 ns, the pulse frequency was 10 Hz, and the laser wavelength was 532 nm. The laser incident energy was 20 μJ. The material has a nonlinear optical property similar to the reverse saturation absorption of Example 1, and the normalized transmittance is reduced to 0.68, so the metal porphyrin-pyrrolopyrrolidone conjugated organic compound PMg-4DPP has a laser limiting effect and can be used for laser protection.

[0123] Example 4

[0124] The structural formula of the metal porphyrin-pyrrolopyrrolidone conjugated organic compound of this example is as follows:

[0125]

[0126] The synthesis route of the metal porphyrin-pyrrolopyrrolidone conjugated organic compound PMg-2DPP is similar to that of Example 1, except that all the Zn in the porphyrin structure in the synthesis route is replaced by Mg. The specific synthesis route is as follows:

[0127]

[0128] Compound nuclear magnetic resonance 1 The H NMR and infrared characterization results are similar to those of Example 2, and the ultraviolet absorption spectrum is similar to that of Example 2, showing a wide intramolecular charge transfer absorption band.

[0129] The nonlinear optical properties of the metal porphyrin-pyrrolopyrrolidone conjugated organic compound PMg-2DPP:

[0130] PMg-2DPP was dissolved in 1,1,2,2-tetrachloroethane, loaded into a 1 mm quartz cuvette, and its linear transmittance at a wavelength of 532 nm was adjusted to 70%. The nonlinear optical properties of the material were tested by Z-scan technology. The test laser was a Nd:YAG pulse laser, the pulse width was 4 ns, the pulse frequency was 10 Hz, and the laser wavelength was 532 nm. The laser incident energy was 20 μJ. The material has a nonlinear optical property similar to the reverse saturation absorption of Example 2, and the normalized transmittance is reduced to 0.73, so the metal porphyrin-pyrrolopyrrolidone conjugated organic compound PMg-2DPP has a laser limiting effect and can be used for laser protection.

[0131] Comparative Example 1

[0132] The structural formula of this comparative example PZn-4Th is as follows:

[0133]

[0134] The synthetic route of the PZn-4Th is as follows:

[0135]

[0136] The nonlinear optical properties of the metalloporphyrin-pyrrolopyrrolidone conjugated structure organic compound PZn-4Th:

[0137] PZn-4Th was dissolved in 1,1,2,2-tetrachloroethane, loaded into a 1mm quartz cuvette, and its linear transmittance at a wavelength of 532nm was adjusted to 70%.

[0138] The nonlinear optical properties of the material were tested by Z-scan technology. The test laser was a Nd:YAG pulse laser, the pulse width was 4ns, the pulse frequency was 10Hz, the laser wavelength was 532nm, and the laser incident energy was 20μJ. As shown in Figure 3 the material had a similar reverse saturation absorption nonlinear optical property to that of Example 1, the normalized transmittance was reduced to 0.85, and compared with the example, the compound had weak nonlinear optical properties.

[0139] Comparative Example 2

[0140] The structural formula of the metalloporphyrin PZn-2Th of the present comparative example is as follows:

[0141]

[0142] The synthetic route of the PZn-2Th is as follows:

[0143]

[0144] The nonlinear optical properties of the metalloporphyrin-pyrrolopyrrolidone conjugated structure organic compound PZn-2Th:

[0145] PZn-2Th was dissolved in 1,1,2,2-tetrachloroethane, loaded into a 1mm quartz cuvette, and its linear transmittance at a wavelength of 532nm was adjusted to 70%.

[0146] The nonlinear optical properties of the material were tested by Z-scan technology. The test laser was a Nd:YAG pulse laser, the pulse width was 4ns, the pulse frequency was 10Hz, the laser wavelength was 532nm, and the laser incident energy was 20μJ. The material had a similar reverse saturation absorption nonlinear optical property to that of Comparative Example 1, the normalized transmittance was reduced to 0.87, and compared with the example, the compound had weak nonlinear optical properties.

[0147] Obviously, the above embodiments of the present application are merely exemplary and are not intended to limit the embodiments of the present application. Based on the above description, other different forms of changes or variations can be made by those skilled in the art, and it is impossible to enumerate all the embodiments here. Any obvious changes or variations derived from the technical solutions of the present application are still within the protection scope of the present application.

Claims

1. Use of a nonlinear optical material in laser amplitude limiting, characterized in that, The nonlinear optical material is prepared from a metal porphyrin-pyrrolopyrrolidone conjugated compound having the structure shown in Formula I or Formula II: (AND), (II); wherein R1is selected from , * indicates the point of attachment to the carbon-carbon triple bond; represents an aromatic group; R represents an alkyl group; M represents a heavy metal atom; In the application, the laser used is a pulse laser; the pulse width of the pulse laser is 4-8 ns, the pulse frequency is 10 Hz, and the wavelength is 532 nm.

2. Use according to claim 1, characterized in that, said R1is selected from any one of , , , and ; * indicates the point of attachment to the carbon-carbon triple bond.

3. Use according to claim 1, characterized in that, The alkyl group is selected from a linear alkyl group or a branched alkyl group; The linear alkyl group is a C1-C12 linear alkyl group; The branched alkyl group has a structural formula of wherein x, n, and m are each independently selected from positive integers from 1 to 12.

4. Use according to claim 1, characterized in that, The heavy metal atom is selected from one of Zn, Mg, Pd, and Cu.

5. Use according to any one of claims 1 to 4, characterized in that, The preparation method of the metal porphyrin-pyrrolopyrrolidone conjugated compound comprises the following steps: a compound shown in Formula I-1 or Formula II-1 (I-1)、 (II-1) is subjected to a trimethylsilane reaction to obtain a compound shown in Formula I-2 or II-2 (I-2)、 (II-2); is subjected to a sonogashira coupling reaction, separation and purification to obtain the metal porphyrin-pyrrolopyrrolidone conjugated compound; (III) wherein R' is selected from -Br or -I; The preparation of the compound shown in Formula I-1 comprises the following steps: The , M and R are as defined in claim 1, respectively.

6. Use according to claim 5, characterized in that, pyrrole and 3-trimethylsilyl propynal are reacted to obtain a porphyrin derivative; The porphyrin derivative is then metallized to obtain the compound shown in Formula I-1; and / or The preparation of the compound shown in Formula II-1 comprises the following steps: 2,2'-dipyrrylmethane and 3-trimethylsilyl propynal are reacted to obtain a porphyrin derivative; The porphyrin derivative is then metallized to obtain the compound shown in Formula II-1. The reaction temperature of pyrrole and 3-trimethylsilyl propynal is -90~-70℃, and the reaction time is 12-24 h; and / or 7. Use according to claim 6, characterized in that, The reaction temperature of 2,2'-dipyrrylmethane and 3-trimethylsilyl propynal is 10-30℃, and the reaction time is 12-24 h. ​

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