CN113845900B - Porphyrin dimer graphene nonlinear composite material and preparation and application thereof - Google Patents
Porphyrin dimer graphene nonlinear composite material and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a porphyrin dimer graphene nonlinear composite material, a preparation method and an application thereof, wherein porphyrin dimer is compounded on the surface of graphene through pi-pi stacking effect, and the porphyrin dimer has longer excited state service life and enhanced anti-saturation absorption, so that a novel nonlinear enhanced nanosecond graphene nonlinear composite material is constructed. In the present invention, beta-o-diaminoporphyrin forms an example of porphyrin dimer linked through a pyrazine ring by self-condensation reaction with diethyl oxalate. The conjugation and delocalization system of dimer pi-electron expansion not only enhances the anti-saturation absorption performance of porphyrin, but also enhances pi-pi stacking effect and electron/energy transmission efficiency between the porphyrin and graphene, thereby enhancing the nonlinear performance of the composite material in the nanosecond laser field. Compared with the traditional material, the material has very strong reference significance for preparing a more efficient nanosecond nonlinear optical element.
Description
Technical Field
The invention belongs to the technical field of organic-inorganic composite materials, and relates to a porphyrin dimer graphene nonlinear composite material, and preparation and application thereof.
Background
Since 2004, geim and Novoselov have found graphene, graphene has attracted considerable attention worldwide. Graphene is a very typical two-dimensional material, and single-layer graphene is formed by sp 2 The hybridized carbon atom composition has high conductivity and excellent photoelectric property. However, graphene is severely limited in its further applications due to its insolubility in water and most organic solvents. One effective strategy to solve the solubility problem is to combine graphene with a suitable functional chromophore. Porphyrin is a dye organic molecule with rich characteristics, and because of a highly conjugated electronic system and a smaller band gap, the porphyrin and the derivatives thereof are widely applied to the fields of medical diagnosis, photodynamic therapy, optical bionic systems, nonlinearity and the like. In order to further develop the application potential of graphene in the nonlinear field, in particular to meet the development requirement of an efficient optical limiter, porphyrin-functionalized graphene nanomaterial appears in the research of the nonlinear optical field in a covalent and non-covalent manner. Wherein functionalization occurs non-covalently, e.g. by pi-pi stacking effect to form nano-particlesRice composites are one of the most widely used methods. Compared with covalent connection, the pi-pi electron stacking effect does not damage the structural integrity of the graphene layer, and meanwhile, graphene can form a more stable dispersion system through compounding with porphyrin, so that rapid sedimentation and aggregation are avoided. Furthermore, the reported work demonstrates that the nonlinear optical properties of porphyrin-graphene nanocomposites are much greater than their respective components due to synergistic effects of a variety of nonlinear optical mechanisms, including nonlinear dispersion of graphene, reverse saturation absorption of porphyrin, and photoinduced electron/energy transfer from porphyrin to graphene.
In the research of the porphyrin graphene composite material, the selection of porphyrin with better nonlinear performance is also an important angle and a method for improving the nonlinear performance of the porphyrin graphene composite material. Among them, porphyrin polymers with pi-electron delocalized extension systems are of particular interest due to their greater nonlinear optical coefficients. However, due to the rapid nonlinear optical response time of porphyrin polymers, porphyrin polymers are often used in the field of femtoseconds, and current research on nanosecond nonlinear optical properties of graphene composite materials is limited to porphyrin monomers. Therefore, porphyrin dimer graphene nanocomposite materials with long response times are expected to exhibit more excellent nonlinear optical properties in the nanosecond field.
The present invention has been made in view of the above background.
Disclosure of Invention
The invention aims to provide a porphyrin dimer graphene nonlinear composite material, and preparation and application thereof.
The aim of the invention can be achieved by the following technical scheme:
one of the technical schemes of the invention provides a porphyrin dimer graphene nonlinear composite material which is formed by interaction of porphyrin dimer and graphene through pi-pi stacking effect.
Further, the porphyrin dimer is formed by connecting two porphyrin monomers through a pyrazine ring.
According to the second technical scheme, the invention provides a preparation method of a porphyrin dimer graphene nonlinear composite material, wherein tetraphenylporphyrin and acid-catalyzed copper nitrate are subjected to metallization and nitration simultaneously to obtain 2-nitrotetraphenylporphyrin copper 2. Then with the help of 4-amino-4H-1, 2, 4-triazole, amino groups are introduced at adjacent beta-position nitro groups of the copper porphyrin 2, so that copper porphyrin 3 with one amino group and one nitro group distributed at two adjacent beta-positions is formed. Copper porphyrin 3 is de-copper ion by strong acid and then re-metallized with zinc to obtain zinc porphyrin 4. Zinc porphyrin 4 reduced with 10% pd/C and sodium borohydride gave zinc o-diaminoporphyrin 5 which was unstable in air. The porphyrin zinc 5 undergoes self-condensation reaction by means of diethyl oxalate to obtain porphyrin dimer 1a. Porphyrin dimer 1a and the surface of graphene are subjected to pi-pi stacking action to prepare the porphyrin dimer graphene nonlinear composite material G-1a nanocomposite.
Specifically, the preparation method of the invention can comprise the following steps:
(1) Dissolving tetraphenylporphyrin in dichloromethane solution, adding copper acetate dissolved in a mixed acid solution in advance, and stirring for reaction to obtain 2-nitro-tetraphenylporphyrin copper;
(2) 2-nitro-tetraphenylporphyrin copper, 4-amino-4H-1, 2, 4-triazole and KOH are reacted in a mixed solution of toluene and ethanol, and reaction products are separated to obtain 2-nitro-3-amino-tetraphenylporphyrin copper;
(3) Dissolving 2-nitro-3-amino-tetraphenylporphyrin copper in dichloromethane solution, dropwise adding a mixture of concentrated sulfuric acid and trifluoroacetic acid, stirring and pouring ice water after quick reaction, collecting an organic phase, adding zinc acetate, continuously stirring and reacting, and separating a reaction product to obtain 2-nitro-3-amino-tetraphenylporphyrin zinc;
(4) Dissolving 2-nitro-3-amino-tetraphenylporphyrin zinc in a dichloromethane and methanol solution, adding palladium carbon, stirring uniformly, continuously adding sodium borohydride, reacting under the monitoring of thin layer chromatography, and separating a reaction product to obtain 2, 3-diaminoporphyrin zinc;
(5) Diethyl oxalate is added into a dichloromethane solution of 2, 3-diaminoporphyrin zinc, and the porphyrin dimer 1a is obtained through reaction under the protection of nitrogen;
(6) And dispersing graphene solid in DMF (dimethyl formamide) by ultrasonic, adding porphyrin dimer 1a into the mixture, continuing ultrasonic, stirring at normal temperature for reaction, filtering and washing to obtain a target product.
Further, in the step (1), the mixed acid solution is prepared from glacial acetic acid and acetic anhydride according to a volume ratio of 1: 5-7. Meanwhile, the stirring reaction is carried out at room temperature for about 16 hours, the reaction process is finished under the monitoring of Thin Layer Chromatography (TLC), and the product has higher polarity than the raw materials and has no red fluorescence.
Further, in the step (1), the molar ratio of tetraphenylporphyrin to copper acetate is 1: (2.5-3).
Further, in the step (2), the molar ratio of the copper 2-nitro-tetraphenylporphyrin to the 4-amino-4H-1, 2, 4-triazole is 1.25: 30-40; the volume ratio of toluene to ethanol is 250-350:15. In this reaction, KOH is generally added in excess.
Further, in the step (3), the addition amount ratio of the copper 2-nitro-3-amino-tetraphenylporphyrin, methylene dichloride, concentrated sulfuric acid, trifluoroacetic acid and zinc acetate is (1.0-1.2) mmol: (30-50) mL: (40-60) mL: (5-10) mmol. Here, the concentration of the concentrated sulfuric acid is preferably 98.3%. After the reaction is finished, the mixture is quickly poured into a large amount of ice water, the reaction time is 10-15min, and carbonization cannot be prevented excessively. After copper removal, the 2-nitro-3-amino-tetraphenylporphyrin copper is directly complexed with zinc ions through a zinc acetate reaction.
Further, in the step (4), the ratio of the addition amounts of zinc 2-nitro-3-amino-tetraphenylporphyrin, palladium on carbon and sodium borohydride was 0.54mmol: (500-800) mg: (10-15) mmol. The reaction is carried out at normal temperature under TLC monitoring, the reaction time is about 2 hours, and after the reaction is finished, the crude product is directly put into the next step without a fine purification process due to unstable product. The palladium carbon may be 10% palladium carbon (10% herein means mass fraction of palladium).
Further, in the step (5), the molar ratio of the zinc 2, 3-diamino-tetraphenylporphyrin to the diethyl oxalate is 0.54: (10-15). Here, the reaction process is specifically: firstly, reacting for 5-7 h at 50-70 ℃, and then reacting for 7-9 h at normal temperature.
Further, in the step (6), the graphene solid is fully sonicated for 3 hours, and then porphyrin dimer 1a is added. Meanwhile, the mass ratio of graphene solid to porphyrin dimer 1a may be about 1:4 to 6, preferably 1:5.
The third technical scheme of the invention provides application of the porphyrin dimer graphene nonlinear composite material in the nanosecond visible light field.
According to the nonlinear nanocomposite, porphyrin dimer 1a and graphene are obtained by means of pi-pi stacking effect through a physical mixing method, van der Waals force between the graphene and the porphyrin plane is enhanced through a conjugated plane increased by 1a, and therefore electron interaction between the porphyrin dimer and the graphene is enhanced, and an example of three-order nonlinear enhanced organic-inorganic composite is obtained.
In the nanocomposite, diaminoporphyrin forms a pyrazine ring-linked porphyrin dimer by self-condensation reaction. The pyrazine ring enlarges the delocalization degree of porphyrin electrons, increases the energy level number of dimeric porphyrin, and increases the possibility of excited state transition, so that 1a has stronger anti-saturation absorption performance than porphyrin monomers. Compared with the traditional material, the prepared material has more enhanced nonlinear optical performance in the nanosecond visible light field, and has very strong reference significance for preparing nonlinear optical elements in the nanosecond field.
The nanocomposite has broadband linear absorption at 375-800nm, characteristic absorption at 402,501 and 600nm, and fluorescence quenching efficiency of 82% compared with that of 1a.
Compared with the prior art, the invention has the following advantages:
1. the composite material not only has broadband linear absorption of graphene at 375-800nm, but also has split solet band absorption and enhanced Q band absorption of porphyrin dimer which is red shifted by about 2 nm.
2. The fluorescence quenching efficiency of the composite material relative to porphyrin reaches 82%, and the effective electron transfer and transmission efficiency between graphene and porphyrin are proved through pi-pi stacking effect.
3. Porphyrin dimer 1a has an excited state lifetime on the order of nanoseconds and enhanced anti-saturation absorption capacity.
4. The composite material has enhanced nonlinear absorption performance compared with the parent material and porphyrin monomer under the irradiation of the laser of 532nm and 12ns nanosecond.
Drawings
FIG. 1 is a photograph of the preparation route and dispersibility of the porphyrin dimer graphene nanocomposite G-1a prepared by the present invention.
FIG. 2 shows the results of a scanning electron microscope (G, G-1 a) and a reference material graphene of the porphyrin dimer graphene nanocomposite prepared by the method.
FIG. 3 shows (a) an infrared spectrum and (b) a Raman spectrum of the porphyrin dimer graphene nanocomposite G-1a and graphene serving as a reference material thereof.
FIG. 4 shows (a) linear absorption spectrum and (b) fluorescence emission spectrum of porphyrin dimer and graphene nanocomposite G-1a and precursor material porphyrin dimer 1a, graphene G prepared by the present invention.
FIG. 5 shows the nonlinear optical absorption spectra (left) and Jablonski energy level spectra (right) of porphyrin dimer graphene nanocomposite G-1a and precursor material porphyrin dimer 1a, graphene G prepared by the invention under a laser of 532nm and 12 ns.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
The raw materials in the following examples include graphene all from reagent companies such as exploration platform, an Naiji, carbofuran, etc., wherein synthetic methods for tetraphenylporphyrin are referred to in the literature (ostowski, s., grzyb, s. (2012). Directβ -amination reaction in porphyrin systems-a simple route to compounds containing two nitrogen substituents at both β -positions of the same pyrrole unit.tetrahedron Letters,53 (47), 6355-6357.)
The remainder, unless specifically stated, is indicative of a conventional commercially available feedstock or conventional processing technique in the art.
Example 1:
referring to fig. 1, the present embodiment provides a method for preparing a porphyrin dimer graphene nonlinear composite material:
the first step: preparation of 2-nitro-tetraphenylporphyrin copper 2.
Unlike the conventional method, the method of this example combines two steps of free radical copper porphyrin ion metallization and beta-position nitration, using acidified Cu (NO 3 ) 2 ·3H 2 O is completed once. Tetraphenylporphyrin (1.23 g,2.00 mmol) was dissolved in 2000mL dichloromethane, cu (NO) 3 ) 2 ·3H 2 O (1.33 g,5.52 mmol) was dissolved in a mixed solution of glacial acetic acid and acetic anhydride (volume ratio 1:6, 140 mL). The two solutions were mixed and stirred at room temperature for 16h, and monitored by Thin Layer Chromatography (TLC) during the reaction until complete consumption of the starting material, while the formation of new spots with large polarity and no fluorescence was observed. After the reaction is finished, the obtained mixture is washed by deionized water to remove a large amount of acid, and then saturated NaHCO is used 3 The collected organic layers were washed sequentially with solution (2X 500 mL) and deionized water. Finally, the organic layer is arranged on Na 2 SO 4 Drying, and distilling under reduced pressure to remove the solvent. Further purification by silica gel column chromatography (eluent: dichloromethane/petroleum ether=1:2) afforded copper (II) (2) 2-nitro-5, 10,15, 20-tetraphenylporphyrin (936 mg, 65% yield). (copper porphyrin 2 (i.e., copper 2-nitro-tetraphenylporphyrin described above) and copper porphyrin 3 mentioned below cannot be used since copper ion-metallized porphyrin is paramagnetic 1 H NMR confirmed that characterization was only performed by MALDI-TOF-MS. )
MS(MALDI-TOF):m/z calcd for C 44 H 27 CuN 5 O 2 721.26,found 721.75[M] +
And a second step of: preparation of copper 2-nitro-3-amino-tetraphenylporphyrin 3.
Copper porphyrin 2 (900 mg,1.25 mmol) was dissolved in 300mL of toluene, 4-amino-4H-1, 2, 4-triazole (3.11 g,37.2 mmol) was dissolved in 15mL of ethanol, and after mixing the two solutions, the reaction system was heated to 90 ℃. To be stable in temperatureAfter that, KOH (6.92 g,123 mmol) was added and the system was further heated to 110 ℃. TLC chlorin was monitored until complete consumption of starting copper porphyrin 2. After the reaction is finished, the mixture is poured into cold water, the organic layer of the mobile phone is extracted by methylene dichloride, and the mobile phone is washed for multiple times by deionized water and Na 2 SO 4 Drying and distilling under reduced pressure to remove the solvent. Further purification by silica gel column chromatography using methylene chloride/petroleum ether (1:1) as eluent gave copper 2-nitro-3-amino-tetraphenylporphyrin (i.e. copper porphyrin 3, 823mg, 1.13 mmol) in 90% yield.
MS(MALDI-TOF):m/z calcd for C 44 H 28 CuN 6 O 2 735.16,found 735.77M] +
And thirdly, preparing the 2-nitro-3-amino-tetraphenylporphyrin zinc 4.
Copper porphyrin 3 (733 mg,1 mmol) was dissolved in 35mL of dichloromethane, to which was added a mixed solution of 35mL of concentrated sulfuric acid and 50mL of trifluoroacetic acid dropwise rapidly. After vigorous stirring at room temperature for 10-15 minutes, the reaction was poured rapidly into 2000mL of cold water. Dichloromethane extraction and organic layer was saturated NaHCO 3 The aqueous solution and deionized water were washed sequentially. Anhydrous Na 2 SO 4 And (5) drying to obtain a dark green organic solution of the target initial product. Zn (OAc) was added thereto without further purification 2 (1.28 g,7.00 mmol) in methanol (15 mL) was stirred overnight at ambient temperature. After the reaction, the solvent was distilled off under reduced pressure, and the green component was collected by silica gel chromatography using methylene chloride/petroleum ether (3:2) as eluent to give zinc 2-nitro-3-amino-tetraphenylporphyrin 4 (515 mg,0.70 mmol) in 90% yield.
1 H NMR(600MHz,CHCl 3 -dδ(ppm)):8.96(1H,d,J＝15.0Hz,H-pyrrole),8.88(1H,d,J＝15.0Hz,H-pyrrole),8.72(1H,d,J＝15.0Hz,H-pyrrole),8.69(1H d,J＝15.0Hz,H-pyrrole),8.59(1H,d,J＝15.0Hz,H-pyrrole),8.43(1H,d,J＝15.0Hz,H-pyrrole),8.18-8.01(10H,m,H-phenyl),7.90-7.77(8H,m,H-phenyl),6.89(2H,br s,NH 2 )。MS(MALDI-TOF):m/z calcd for C 44 H 28 ZnN 6 O 2 736.21,found 736.34[M] +
Fourth step: preparation of zinc 2, 3-diamino-tetraphenylporphyrin 5
Zinc 2-nitro-3-amino-tetraphenylporphyrin 4 (400 mg,0.54 mmol) was dissolved in a mixed solution of methylene chloride and methanol (volume ratio 10:1, 220 mL). N (N) 2 After bubbling for 20 minutes, 600mg of 10% palladium on carbon was added. The system is N 2 Stirring thoroughly for 10 min under atmosphere, and slowly adding NaBH in batches after the system is uniformly dispersed 4 (534 mg,14.4 mmol) until zinc 2-nitro-3-amino-tetraphenylporphyrin 4 was completely consumed (about 2 h) under TLC monitoring. After the reaction, the reaction system was preliminarily filtered through a celite-packed flash column with methylene chloride as eluent (100 mL) to obtain a crude product of 2, 3-diamino-tetraphenylporphyrin zinc 5. Because the beta-o-diaminoporphyrin is unstable in air, the crude product of the zinc 2, 3-diamino-tetraphenylporphyrin 5 is directly put into the next reaction without further purification and characterization.
Fifth step: preparation of porphyrin dimer 1a.
To a solution of the crude zinc 2, 3-diamino-tetraphenylporphyrin 5 (0.54 mmol) in methylene chloride under nitrogen was added diethyl oxalate (1.9 mL,14.0 mmol) and 20mL of methanol. The system was stirred at 60℃for 6h followed by 8h at ambient temperature. After the reaction is finished, the organic solvent is removed by reduced pressure distillation, column chromatography purification is carried out by taking methylene dichloride/petroleum ether (volume is 2:3) as an eluent, and the reddish brown component with smaller polarity is collected. Further recrystallization from methylene chloride/methanol gave porphyrin dimer 1a (385 mg,0.28 mmol) in 40% yield.
1 H NMR(600MHz,CHCl 3 -d,δ(ppm)):8.86(8H,d,J＝16Hz,H-pyrrole)，8.68(4H,d,J＝16Hz,H-pyrrole)，8.33-8.04(20H,m,H-phenyl)，7.80-7.56(20H,m,H-phenyl)。MS(MALDI-TOF):m/z calcd for C 88 H 52 Zn 2 N 10 1380.21,found 1381.80[M] +
Sixth, preparation of porphyrin dimer graphene nonlinear composite material G-1a
Graphene (20 mg) was dispersed in 30mL DMF for sufficient pre-sonication for approximately 3 hours to give a uniform suspension of graphene. Porphyrin dimer 1a (100 mg) was added thereto and sonication was continued for 1h. After sonication was completed, the mixture was stirred at room temperature overnight. After the reaction, the mixture was filtered through a polytetrafluoroethylene film (0.22 μm), and the obtained solid was thoroughly washed with DMF and tetrahydrofuran, and dried in a vacuum oven for 24 hours to obtain a target composite product porphyrin dimer graphene nanocomposite G-1a (22 mg).
Taking a proper amount of porphyrin dimer graphene nanocomposite G-1a, and directly performing Scanning Electron Microscope (SEM), total reflection infrared (FTIR), raman spectrum (Raman) and photophysical research (steady-state absorption, fluorescence and z-scan research) on the supernatant after sufficient ultrasonic and centrifugal treatment. The inset above G-1a in FIG. 1 shows that pure graphene, porphyrin dimer 1a and porphyrin dimer graphene nanocomposite G-1a are well dispersed in DMF and allowed to stand for three days. Unlike graphene which is easy to precipitate, the porphyrin dimer graphene nanocomposite G-1a still presents a relatively uniform suspension after three days, and provides preliminary evidence for successful adhesion of porphyrin dimer 1a to the graphene surface.
SEM testing provided topographical information for pure graphene G and porphyrin dimer graphene nanocomposite G-1a, as shown in fig. 2a and 2 b. Unfunctionalized graphene is extremely easy to agglomerate and difficult to uniformly disperse in an organic solvent. After modification with porphyrin dimer 1a, the number of graphene layers was significantly reduced relative to fig. 2a, which is consistent with the dispersion results in DMF in fig. 1. To further obtain elemental composition information, elemental mapping images of porphyrin dimer graphene nanocomposite material G-1a are shown in fig. 2 (c) to 2 (f). The distribution of N and Zn atoms is relatively small compared to the C and O present in large amounts, and the side surface indicates that porphyrin dimer functionalization of the graphene surface is effective.
The total reflection infrared spectra of pure graphene, porphyrin dimer 1a and porphyrin dimer graphene nanocomposite G-1a are shown in fig. 3 a. In the spectrum of pure graphene, except at 1682cm -1 No significant signal was found outside the weak absorption that is centered, indicating that some carbonyl groups may remain with the purchased graphene. The infrared spectrum of porphyrin dimer 1a shows the characteristic absorption of porphyrin compounds: 1220 and 1085cm -1 Corresponding to the stretching vibration of pyrrole C-N in the center of porphyrin ring,1645cm -1 the absorption peak at corresponds to the c=n stretching vibration in the pyrazine ring between the two porphyrin monomers. Furthermore, it is positioned at 1458cm -1 And 660-900cm -1 The peaks at these correspond to the stretching vibration and out-of-plane bending vibration of pyrrole C-H on the plane of porphyrin dimer, respectively. After the graphene is functionalized by the porphyrin dimer 1a, the infrared spectrum is combined with characteristic absorption peaks of the graphene and the porphyrin dimer 1a, so that successful attachment of the porphyrin dimer 1a on the surface of the graphene is further confirmed.
Fig. 3b shows raman spectral information for pure graphene, porphyrin dimer 1a and porphyrin dimer graphene nanocomposite G-1 a. For pure graphene G, there are mainly two typical characteristic shifts: d peak, located at 1300-1500cm -1 The peak G is 1500-1700cm -1 . The presence of the D peak generally results from disordered modes and sp of the surface lattice 3 The recombination of carbon atoms, and therefore the degree of defects and disorder of the graphene surface, while the G peak is generally associated with sp 2 The composite carbon atoms are related and originate from planar vibration of a tangential mode of the graphene surface. The raman signal of porphyrin dimer 1a is more complex than that of graphene. At 1600, 1541, 1402, 1357 and 1205cm -1 The Raman shift as the center corresponds to the C-C bond v (C α C m ),v(C β C β ) V (pyrole-half-ring), v (pyrole-quater-ring) and v (C) m -ph) A g And B 1g And (5) stretching and vibrating. Physical mixing severely destroys the structural integrity of the graphene crystalline structure compared to covalent bonding, so that the graphene composite material through covalent bonding is typically accompanied by an intensity ratio of D-band and G-band (I D /I G ) By pi-pi stacking interaction, the obtained porphyrin dimer graphene nanocomposite G-1a has I D /I G The ratio remains substantially unchanged, meaning that the graphene planar structure is not destroyed. Meanwhile, the characteristic displacement position of 1a on the Raman curve of the porphyrin dimer graphene nanocomposite G-1a is changed, and strong resonance occurs between a singlet excited state derived from porphyrin and graphene, so that high electron coupling between the graphene and the porphyrin dimer is verified.
Fig. 4a shows the uv-visible spectra of pure graphene, porphyrin monomer ZnTPP, porphyrin dimer 1a and porphyrin dimer graphene nanocomposite G-1 a. Pure graphene G exhibits a typical broadband unstructured absorption, gradually decreasing in absorption intensity from 300nm to 800 nm; znTPP shows a characteristic absorption band of porphyrin monomers, for example, a strong B (solet) band absorption at 423nm and weaker Q band absorption at 559nm and 601 nm. Whereas for porphyrin dimer 1a B appears in near-UV and visible light regions, respectively y (402nm)、B x (501 nm) and Q x (λ max At 600 nm) three distinct absorption peaks. Porphyrin dimer 1a compared with porphyrin monomer ZnTPP, the Q-band (Q x ) Slightly red-shifted, and the strength is obviously enhanced. The B band is split into two absorption bands, B y And B x . The change between ZnTPP and 1a is mainly due to the fact that by condensation reaction, the pi-electron delocalization system is extended by the connection between two porphyrin monomers through the conjugated pyrazine ring. e, e g The degeneracy of the orbitals, exciton coupling between transition dipole moments, and coulomb interactions greatly disrupt the electron distribution on the porphyrin ring, resulting in a change in steady state absorption, similar to the previously reported results for fused porphyrin dimers. The electron absorption spectrum of the porphyrin dimer graphene nanocomposite G-1a shows the combination of component absorption spectra, and the weaker low-energy Q band absorption on the porphyrin dimer graphene nanocomposite G-1a is slightly red shifted relative to 1a, so that the component 1a and graphene generate effective electron space interaction through pi-pi accumulation.
The interaction between porphyrin dimer 1a and graphene can be further verified by fluorescence experiments. Materials with D-a structures are often accompanied by efficient photoinduced energy and electron transfer processes. As shown in FIG. 4b, under 501nm excitation, porphyrin dimer 1a showed fluorescence characteristic peaks mainly at 635nm,710nm accompanied by a weaker shoulder. Since graphene itself does not show a fluorescence signal, the fluorescence signal of the porphyrin dimer graphene nanocomposite G-1a can be determined to originate from the porphyrin dimer 1a attached to the graphene surface. After the graphene is functionalized, the porphyrin dimer 1a plays a role of an antenna and is excited to a singlet excited state, and as the graphene acts as an electron acceptor, energy in the porphyrin singlet excited state does not directly emit fluorescence to return to a ground state, but is transferred to graphene at a lower energy level through intra-system energy transfer, so that a significant fluorescence quenching phenomenon (about 82%) is caused, and direct evidence is provided for effective photoinduced electron/energy transfer between the 1a component and the graphene.
The suspensions of porphyrin monomer ZnTPP, porphyrin dimer 1a, graphene G and G-1a nanocomposite in DMF were subjected to open-cell z-scan testing under irradiation of a pulsed laser of 532nm,12ns, the results of which are shown in FIG. 5 (left). The method can fully explore the nonlinear optical properties of the precursor and the porphyrin dimer graphene nanocomposite G-1a, in particular to the difference of anti-saturation absorption properties between porphyrin monomers and pyrazine ring connected porphyrin dimer 1a. The linear transmittance of all samples was kept uniform (about 65%) by adjusting the concentration. Pure DMF has no detectable nonlinear optical properties, indicating that the contribution of the solvent is negligible and the observed absorption is attributable to the solute. Furthermore, the effective nonlinear absorption coefficient (beta) can be further deduced by using curve fitting z-scan data eff ). At the z=0 position (at the lens focus), the normalized transmittance (T) of graphene G, znTPP, porphyrin dimer 1a and porphyrin dimer graphene nanocomposite G-1a under 6.3 μj laser irradiation was reduced from 100% to 75%, 69%, 51% and 45%, respectively. The nonlinear absorption coefficients are 14.02 (G), 16.18 (ZnTPP), 21.36 (1 a) and 27.52 (G-1 a) cm/GW in order. Interestingly, from porphyrin monomer ZnTPP to porphyrin dimer 1a, the normalized transmittance was reduced from 75% to 51%. It is known from reported work that under ns laser conditions, the efficiency of reverse saturation absorption depends on the ratio of the excited state absorption cross section to the ground state absorption cross section, i.e. the larger the excited state absorption cross section, the higher the reverse saturation absorption efficiency. For the porphyrin monomer ZnTPP, the reverse saturation absorption, which is dominant in the excited state absorption, is usually composed of a singlet excited state S 1 Transition to higher energy state S 2 、S 3 Triplet excitationState T 1 Transition to T 2 、T n Is determined by the process of (1). The Jablonski energy level diagram of porphyrin monomer ZnTPP and porphyrin dimer 1a is shown in fig. 5 (right). As can be seen in the absorption spectrum of FIG. 5 (left), the B band absorption of porphyrin dimer 1a is split into two absorption B due to pi-electron highly delocalized cleavage y Mix B x . Wherein B is y The energy is higher than the B band of ZnTPP, and the other energy is lower than the B band of ZnTPP. Unlike the three-wire linked fused porphyrin dimer, the pyrazine ring-linked porphyrin dimer 1a has a nanosecond lifetime, which is on the order of magnitude that ensures that a sufficient number of electrons on the porphyrin first singlet excited state can continue to absorb photons to a higher energy level, thus exhibiting a stronger anti-saturation absorption property and an effective light confinement effect. To better evaluate the anti-saturation absorption capacity of porphyrin dimer 1a, the excitation absorption cross section (σ) was further calculated ex ) Absorption cross section with ground state (sigma) 0 ) Is a ratio of (2). Sigma of ZnTPP and 1a ex /σ 0 The ratios were 2.06 and 2.72, respectively, consistent with the above mechanism inferences. Normalized transmittance of porphyrin dimer graphene nanocomposite G-1a at beam focus in all samples tested (T min) The value is lowest (45%) and the nonlinear coefficient is greatest (27.52 cm/GW), indicating that its optical clipping effect is much stronger than that of pure graphene, 1a and porphyrin monomer ZnTPP, and is due to synergistic effects of various mechanisms including nonlinear scattering of graphene, efficient photoelectronic energy transfer between the two components of porphyrin dimer graphene nanocomposite G-1a, especially the greatly enhanced anti-saturation absorption effect of 1a.
Example 2:
in comparison with example 1, the vast majority of the same is found, except that in this example, the mixed acid solution used is prepared from glacial acetic acid and acetic anhydride in a volume ratio of 1:5, mixing; the molar ratio of tetraphenylporphyrin to copper acetate is 1:2.5.
example 3:
in comparison with example 1, the vast majority of the same is found, except that in this example, the mixed acid solution used is prepared from glacial acetic acid and acetic anhydride in a volume ratio of 1:7, mixing; the molar ratio of tetraphenylporphyrin to copper acetate is 1:3.
example 4:
in comparison with example 1, which is largely identical, except that in this example, the molar ratio of copper 2-nitro-tetraphenylporphyrin to 4-amino-4H-1, 2, 4-triazole is 1.25:30; the volume ratio of toluene to ethanol was 250:15.
Example 5:
in comparison with example 1, which is largely identical, except that in this example, the molar ratio of copper 2-nitro-tetraphenylporphyrin to 4-amino-4H-1, 2, 4-triazole is 1.25:40, a step of performing a; the volume ratio of toluene to ethanol was 350:15.
Example 6:
in comparison with example 1, the same operations were carried out in the same manner as in example 1 except that the addition amount ratio of copper 2-nitro-3-amino-tetraphenylporphyrin, methylene chloride, concentrated sulfuric acid, trifluoroacetic acid and zinc acetate was 1.0mmol:30 mL:40mL:5mmol. Example 7:
in comparison with example 1, the same operations were carried out in the same manner as in example 1 except that the addition amount ratio of copper 2-nitro-3-amino-tetraphenylporphyrin, methylene chloride, concentrated sulfuric acid, trifluoroacetic acid and zinc acetate was 1.2mmol:50 mL:60mL:10mmol.
Example 8:
in comparison with example 1, the same operations were carried out in the same manner as in example 1 except that the ratio of the addition amounts of zinc 2-nitro-3-amino-tetraphenylporphyrin, palladium on carbon and sodium borohydride was 0.54mmol:500mg:10mmol.
Example 9:
in comparison with example 1, the same operations were carried out in the same manner as in example 1 except that the ratio of the addition amounts of zinc 2-nitro-3-amino-tetraphenylporphyrin, palladium on carbon and sodium borohydride was 0.54mmol:800mg:15mmol.
Example 10:
in comparison with example 1, the molar ratio of zinc 2, 3-diamino-tetraphenylporphyrin to diethyl oxalate was 0.54, except that in this example: 10. here, the reaction process is specifically: the reaction is carried out for 7 hours at 50 ℃ and then at normal temperature for 7 hours.
Example 11:
in comparison with example 1, the molar ratio of zinc 2, 3-diamino-tetraphenylporphyrin to diethyl oxalate was 0.54, except that in this example: 15. here, the reaction process is specifically: the reaction is carried out for 5 hours at 70 ℃ and then for 9 hours at normal temperature.
Example 12:
most of the same as in example 1, except that in this example, the mass ratio of graphene solids to porphyrin dimer 1a may be about 1:4.
Example 13:
most of the same as in example 1, except that in this example, the mass ratio of graphene solid to porphyrin dimer 1a may be about 1:6.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The porphyrin dimer graphene nonlinear composite material is characterized by being formed by interaction of porphyrin dimer and graphene through pi-pi stacking effect;
the composite material is prepared by the following steps:
(1) Dissolving tetraphenylporphyrin in dichloromethane solution, adding copper acetate dissolved in a mixed acid solution in advance, and stirring for reaction to obtain 2-nitro-tetraphenylporphyrin copper;
(2) Copper 2-nitro-tetraphenylporphyrin and 4-amino-4H-1,2, 4-triazole and KOH react in a mixed solution of toluene and ethanol, and the reaction product is separated to obtain 2-nitro-3-amino-tetraphenylporphyrin copper;
(3) Dissolving 2-nitro-3-amino-tetraphenylporphyrin copper in dichloromethane solution, dropwise adding a mixture of concentrated sulfuric acid and trifluoroacetic acid, stirring and pouring ice water after quick reaction, collecting an organic phase, adding zinc acetate, continuously stirring and reacting, and separating a reaction product to obtain 2-nitro-3-amino-tetraphenylporphyrin zinc;
(4) Dissolving 2-nitro-3-amino-tetraphenylporphyrin zinc in a dichloromethane and methanol solution, adding palladium carbon, stirring uniformly, continuously adding sodium borohydride, reacting under the monitoring of thin layer chromatography, and separating a reaction product to obtain 2, 3-diaminoporphyrin zinc;
(5) Diethyl oxalate is added into a dichloromethane solution of 2, 3-diaminoporphyrin zinc, and the porphyrin dimer 1a is obtained through reaction under the protection of nitrogen;
(6) And dispersing graphene solid in DMF (dimethyl formamide) by ultrasonic, adding porphyrin dimer 1a into the mixture, continuing ultrasonic, stirring at normal temperature for reaction, filtering and washing to obtain a target product.
2. The porphyrin dimer graphene nonlinear composite material according to claim 1, wherein the porphyrin dimer is formed by connecting two porphyrin monomers through a pyrazine ring.
3. The method for preparing the porphyrin dimer graphene nonlinear composite material according to claim 1 or 2, which comprises the following steps:
(1) Dissolving tetraphenylporphyrin in dichloromethane solution, adding copper acetate dissolved in a mixed acid solution in advance, and stirring for reaction to obtain 2-nitro-tetraphenylporphyrin copper;
(2) Copper 2-nitro-tetraphenylporphyrin and 4-amino-4H-1,2, 4-triazole and KOH react in a mixed solution of toluene and ethanol, and the reaction product is separated to obtain 2-nitro-3-amino-tetraphenylporphyrin copper;
(3) Dissolving 2-nitro-3-amino-tetraphenylporphyrin copper in dichloromethane solution, dropwise adding a mixture of concentrated sulfuric acid and trifluoroacetic acid, stirring and pouring ice water after quick reaction, collecting an organic phase, adding zinc acetate, continuously stirring and reacting, and separating a reaction product to obtain 2-nitro-3-amino-tetraphenylporphyrin zinc;
(4) Dissolving 2-nitro-3-amino-tetraphenylporphyrin zinc in a dichloromethane and methanol solution, adding palladium carbon, stirring uniformly, continuously adding sodium borohydride, reacting under the monitoring of thin layer chromatography, and separating a reaction product to obtain 2, 3-diaminoporphyrin zinc;
(5) Diethyl oxalate is added into a dichloromethane solution of 2, 3-diaminoporphyrin zinc, and the porphyrin dimer 1a is obtained through reaction under the protection of nitrogen;
(6) And dispersing graphene solid in DMF (dimethyl formamide) by ultrasonic, adding porphyrin dimer 1a into the mixture, continuing ultrasonic, stirring at normal temperature for reaction, filtering and washing to obtain a target product.
4. The method for preparing the porphyrin dimer graphene nonlinear composite material according to claim 3, wherein in the step (1), the mixed acid solution is prepared from glacial acetic acid and acetic anhydride according to a volume ratio of 1: 5-7, mixing;
the molar ratio of tetraphenylporphyrin to copper acetate is 1: (2.5-3).
5. The method for preparing a porphyrin dimer graphene nonlinear composite material according to claim 3, wherein in the step (2), 2-nitro-tetraphenylporphyrin copper and 4-amino-4H-1,2, 4-triazole in a molar ratio of 1.25: 30-40 parts; the volume ratio of toluene to ethanol is 250-350:15.
6. The method for preparing a porphyrin dimer graphene nonlinear composite material according to claim 3, wherein in the step (3), the addition amount ratio of 2-nitro-3-amino-tetraphenylporphyrin copper, dichloromethane, concentrated sulfuric acid, trifluoroacetic acid and zinc acetate is (1.0-1.2) mmol: (30-50) mL: (40-60) mL: (5-10) mmol.
7. The method for preparing a porphyrin dimer graphene nonlinear composite material according to claim 3, wherein in the step (4), the addition amount ratio of 2-nitro-3-amino-tetraphenylporphyrin zinc, palladium carbon and sodium borohydride is 0.54mmol: (500-800) mg: (10-15) mmol.
8. The method for preparing a porphyrin dimer graphene nonlinear composite material according to claim 3, wherein in the step (5), the molar ratio of 2, 3-diamino-tetraphenylporphyrin zinc to diethyl oxalate is 0.54: (10-15);
the reaction process comprises the following steps: firstly, reacting for 5-7 hours at 50-70 ℃, and then reacting for 7-9 hours at normal temperature.
9. The method for preparing a porphyrin dimer graphene nonlinear composite material according to claim 3, wherein in the step (6), graphene solid is fully sonicated for 3 hours, and then porphyrin dimer 1a is added.
10. Use of a porphyrin dimer graphene nonlinear composite material according to claim 1 or 2 in the nanosecond visible light field.
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