CN113845900A - 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 and preparation and application thereof. In the invention, beta-ortho-diammine porphyrin forms a porphyrin dimer connected through a pyrazine ring through self-condensation reaction by diethyl oxalate. The dimer pi-electron expanded conjugation and delocalization system not only enhances the anti-saturation absorption performance of porphyrin, but also enhances the pi-pi accumulation effect and the 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 its discovery by geom and Novoselov in 2004, graphene has attracted considerable attention worldwide. Graphene is a very typical two-dimensional material, and single-layer graphene is formed by sp2The hybrid carbon atom has high conductivity and excellent photoelectric property. However, since graphene is insoluble in water and most organic solventsIts further use is severely limited. One effective strategy to address the solubility problem is to combine graphene with a suitable functional chromophore. Porphyrin is a dye organic molecule with rich characteristics, and porphyrin and derivatives thereof are widely applied to the fields of medical diagnosis, photodynamic therapy, optical bionic systems, nonlinearity and the like due to a highly conjugated electronic system and a smaller band gap. In order to further develop the application potential of graphene in the nonlinear field, particularly meet the development requirement of a high-efficiency optical limiter, porphyrin-functionalized graphene nano-material is developed in the research of the nonlinear optical field in a covalent and non-covalent manner. Among them is the one of the most widely used methods of functionalization in a non-covalent manner, such as the formation of nanocomposites by the pi-pi stacking effect. Relative to covalent connection, pi-pi electron stacking does not damage the structural integrity of the graphene layer, and graphene can form a more stable disperse system through compounding with porphyrin, so that rapid sedimentation and aggregation are avoided. Furthermore, reported work has demonstrated 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 scattering of graphene, reverse saturation absorption of porphyrins, and photoinduced electron/energy transfer from porphyrins 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 method for improving the nonlinear performance of the porphyrin graphene composite material. Among them, porphyrin multimers having a pi-electron delocalized extension system are of particular interest because they have a larger nonlinear optical coefficient. However, due to the fast nonlinear optical response time of the porphyrin polymer, the porphyrin polymer is mostly used in the femtosecond field, and the research on the nanosecond nonlinear optical performance of the graphene composite material is limited to the porphyrin monomer. Therefore, the porphyrin dimer graphene nanocomposite material with long response time is expected to have more excellent nonlinear optical performance 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 purpose of the invention can be realized 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 between porphyrin dimer and graphene through a pi-pi stacking effect.
Furthermore, the porphyrin dimer is formed by connecting two porphyrin monomers through a pyrazine ring.
The second technical scheme of the invention provides a preparation method of a porphyrin dimer graphene nonlinear composite material, which comprises the steps of carrying out metallization and nitration reactions on tetraphenylporphyrin and acid-catalyzed copper nitrate simultaneously to obtain 2-nitro copper tetraphenylporphyrin 2. Then, with the help of 4-amino-4H-1, 2, 4-triazole, amino groups are introduced into positions adjacent to the nitro group at the beta position of copper porphyrin 2, so that copper porphyrin 3 with one amino group and one nitro group distributed on two adjacent beta positions respectively is formed. Porphyrin copper 3 is subjected to strong acid copper ion removal and subsequent zinc remetallization to obtain porphyrin zinc 4. The porphyrin zinc 4 is reduced by 10 percent Pd/C and sodium borohydride to obtain ortho-diamino porphyrin zinc 5 which is unstable in air. Porphyrin zinc 5 undergoes a self-condensation reaction with the help of diethyl oxalate to obtain porphyrin dimer 1 a. The porphyrin dimer 1a and the graphene surface are subjected to pi-pi stacking 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 a dichloromethane solution, adding copper acetate dissolved in a mixed acid solution in advance, and stirring for reaction to obtain 2-nitro-copper tetraphenylporphyrin;
(2) reacting 2-nitro-copper tetraphenylporphyrin, 4-amino-4H-1, 2, 4-triazole and KOH in a mixed solution of toluene and ethanol, and separating a reaction product to obtain 2-nitro-3-amino-copper tetraphenylporphyrin;
(3) dissolving 2-nitro-3-amino-tetraphenylporphyrin copper in a dichloromethane solution, dropwise adding a mixture of concentrated sulfuric acid and trifluoroacetic acid, stirring and pouring ice water after rapid 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-zinc tetraphenylporphyrin in dichloromethane and methanol solution, adding palladium carbon, stirring uniformly, continuing adding sodium borohydride, reacting under the monitoring of thin-layer chromatography, and separating a reaction product to obtain 2, 3-zinc diaminoporphyrin;
(5) adding diethyl oxalate into a dichloromethane solution of 2, 3-diaminoporphyrin zinc, and reacting under the protection of nitrogen to obtain a porphyrin dimer 1 a;
(6) and ultrasonically dispersing the graphene solid in DMF (dimethyl formamide), adding porphyrin dimer 1a into the DMF, continuing to perform ultrasonic treatment, stirring the mixture at normal temperature for reaction, filtering and washing the reaction product to obtain a target product.
Further, in the step (1), the mixed acid solution is prepared by mixing glacial acetic acid and acetic anhydride in a volume ratio of 1: 5-7, and mixing. Meanwhile, the stirring reaction is carried out at room temperature for about 16h, the reaction process is completed under the monitoring of Thin Layer Chromatography (TLC), the polarity of the product is larger than that of the raw material, and no red fluorescence exists.
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 parts of; the volume ratio of the toluene to the ethanol is 250-350: 15. In this reaction, KOH is generally added in excess.
Further, in the step (3), the adding amount ratio of the 2-nitro-3-amino-tetraphenylporphyrin copper, the dichloromethane, the concentrated sulfuric acid, the trifluoroacetic acid and the zinc acetate is (1.0-1.2) mmol: (30-50) mL (30-50) mL: (40-60) mL: (5-10) mmol. Here, the concentration of concentrated sulfuric acid is preferably 98.3%. After the reaction is finished, pouring into a large amount of ice water quickly, wherein the reaction time is 10-15min, and the carbonization cannot be prevented too much. After copper is removed from the 2-nitro-3-amino-tetraphenylporphyrin copper, the copper is directly reacted with zinc acetate to complex zinc ions.
Further, in the step (4), the adding amount ratio of the zinc 2-nitro-3-amino-tetraphenylporphyrin to the palladium carbon to the sodium borohydride is 0.54 mmol: (500-800) mg: (10-15) mmol. The reaction is carried out at normal temperature under the monitoring of TLC, the reaction time is about 2h, and after the reaction is finished, the crude product is directly put into the next step without a careful purification process due to the instability of the product. The palladium on carbon may be 10% palladium on carbon (10% herein refers to the mass fraction of palladium).
Further, in the step (5), the molar ratio of the 2, 3-diamino-tetraphenylporphyrin zinc to the diethyl oxalate is 0.54: (10-15). Here, the reaction process is specifically: the reaction is carried out for 5-7 h at 50-70 ℃, and then for 7-9 h at normal temperature.
Further, in the step (6), the graphene solid is fully subjected to ultrasonic treatment for 3 hours, and then the porphyrin dimer 1a is added. Meanwhile, the mass ratio of the graphene solid to the porphyrin dimer 1a can be about 1: 4-6, and preferably 1: 5.
The third technical scheme of the invention provides application of the porphyrin dimer graphene nonlinear composite material in the field of nanosecond visible light.
The nonlinear nanocomposite is obtained by physically mixing porphyrin dimer 1a and graphene by virtue of a pi-pi stacking effect, and van der Waals force between graphene and a porphyrin plane is enhanced through an enlarged conjugated plane of 1a, so that the electronic interaction between the porphyrin dimer and the graphene is enhanced, and the third-order nonlinear reinforced organic-inorganic composite is obtained.
In the nanocomposite, diaminoporphyrin forms porphyrin dimer with pyrazine ring linkage through self-condensation reaction. The pyrazine ring enlarges the delocalization degree of porphyrin electrons, increases the energy level number of dimer porphyrin, thereby increasing the possibility of excited state transition, and leading 1a to have stronger reverse saturation absorption performance than porphyrin monomer. 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 nano composite material has broadband linear absorption at 375-800nm, has characteristic absorption at 402, 501 and 600nm, and has fluorescence quenching efficiency up to 82% compared with 1 a.
Compared with the prior art, the invention has the following advantages:
firstly, the composite material not only has broadband linear absorption of graphene at 375-800nm, but also has split soret band absorption of porphyrin dimer red-shifted by about 2nm and enhanced Q band absorption.
Secondly, the fluorescence quenching efficiency of the composite material relative to porphyrin reaches 82%, and the fact that effective electron transfer and transmission efficiency exists between graphene and porphyrin through a pi-pi stacking effect is verified.
And thirdly, porphyrin dimer 1a has the excited state lifetime of nanosecond level and enhanced reverse saturable absorption capacity.
And fourthly, the composite material has enhanced nonlinear absorption performance compared with the parent material and the porphyrin monomer under 532nm and 12ns nanosecond laser irradiation.
Drawings
FIG. 1 shows a preparation route and a dispersion photograph of porphyrin dimer graphene nanocomposite G-1a prepared by the present invention.
FIG. 2 shows scanning electron micrographs (left: G, right: G-1a) and Mapping results of the porphyrin dimer graphene nanocomposite G-1a and the reference material graphene prepared by the invention.
FIG. 3 shows (a) IR spectra and (b) Raman spectra of porphyrin dimer graphene nanocomposite G-1a and reference material graphene thereof prepared according to the present invention.
Fig. 4 shows (a) a linear absorption spectrum and (b) a fluorescence emission spectrum of the porphyrin dimer graphene nanocomposite G-1a and the precursor material porphyrin dimer 1a prepared by the present invention, and graphene G.
Fig. 5 shows nonlinear optical absorption spectrum (left) and Jablonski energy level spectrum (right) of porphyrin dimer graphene nanocomposite G-1a and precursor material porphyrin dimer 1a, graphene G prepared by the invention under 532nm,12ns laser.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, the raw materials include graphene from research platform, Annagji, Bailingwei, etc., wherein the synthetic method of tetraphenylporphyrin is referred to in the literature (Ostrowski, S., Grzyb, S. (2012), Direct β -amino reaction in porous systems-a simple route to compounds control two n-nitro products of bottom bed β -positions of the sample propyl unit tetrahedron Letters,53 (6347), 55-
The rest of the raw material reagents or treatment techniques, if not specifically mentioned, indicate that the raw materials are all conventional commercial raw materials or conventional treatment techniques in the field.
Example 1:
referring to fig. 1, this embodiment provides a preparation method of a porphyrin dimer graphene nonlinear composite material:
the first step is as follows: preparation of 2-nitro-copper tetraphenylporphyrin 2.
Unlike the conventional method, the method of this example combines the two-step reaction of copper ion metallation and nitration at beta position of radical porphyrin, using acidified Cu (NO)3)2·3H2And O is completed once. Tetraphenylporphyrin (1.23g,2.00mmol) dissolved in 2000mL of dichloromethane, Cu (NO)3)2·3H2O (1.33g,5.52mmol) 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 the progress of the reaction was monitored by Thin Layer Chromatography (TLC) until complete consumption of the starting material, while formation of new spots with high 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 used3The collected organic layers were washed sequentially with solution (2X 500mL) and deionized water. Finally, the organic layer is coated with Na2SO4Drying, and distilling under reduced pressure to remove the solvent. Further purification by silica gel column chromatography (eluent: dichloromethane/petroleum ether ═ 1:2) afforded 2-nitro-5, 10,15, 20-tetraphenylporphyrin copper (II) (2) (936mg, yield 65%). (since copper ion-metallized porphyrins are paramagnetic, copper porphyrin 2 (i.e., the above-mentioned 2-nitro-tetraphenylporphyrin copper) and copper porphyrin 3 mentioned below cannot be used1H NMR confirmed that characterization was only possible by MALDI-TOF-MS. )
MS(MALDI-TOF):m/z calcd for C44H27CuN5O2 721.26,found 721.75[M]+
The second step is that: preparation of 2-nitro-3-amino-tetraphenylporphyrin copper 3.
Copper porphyrin 2(900mg,1.25mmol) was dissolved in 300mL of toluene, 4-amino-4H-1, 2, 4-triazole (3.11g,37.2mmol) was dissolved in 15mL of ethanol, and after mixing the two solutions, the reaction was heated to 90 ℃. After the temperature had stabilized, KOH (6.92g, 123mmol) was added and the system was further heated to 110 ℃. TLC porphyrin was monitored until the starting porphyrin copper 2 was completely consumed. After the reaction is finished, the mixture is poured into cold water, the organic layer of the mobile phone is extracted by dichloromethane, and the organic layer is washed for multiple times by deionized water and Na2SO4Drying, and distilling under reduced pressure to remove the solvent. Further purification by silica gel column chromatography using dichloromethane/petroleum ether (1:1) as eluent gave copper 2-nitro-3-amino-tetraphenylporphyrin (i.e. copper porphyrin 3, 825mg,1.13mmol) in 90% yield.
MS(MALDI-TOF):m/z calcd for C44H28CuN6O2 735.16,found 735.77M]+
And step three, preparing 2-nitro-3-amino-zinc tetraphenylporphyrin 4.
Copper porphyrin 3(733mg,1mmol) was dissolved in 35mL of dichloromethane, and a mixed solution of 35mL of concentrated sulfuric acid and 50mL of trifluoroacetic acid was rapidly added dropwise thereto. After vigorous stirring for 10-15 minutes at room temperature, the reaction was quickly poured into 2000mL of cold water. Dichloromethane extraction, organic layer with saturated NaHCO3The aqueous solution and deionized water were washed sequentially. Anhydrous Na2SO4Drying to obtain a dark green organic solution of the target primary product. Without further purification, Zn (OAc) was added thereto2A solution of (1.28g,7.00mmol) in methanol (15mL) was stirred at room temperature overnight. After the reaction is finished, the solvent is removed by reduced pressure distillation, dichloromethane/petroleum ether (3:2) is taken as an eluent,purification by silica gel chromatography and collection of the green fraction gave 2-nitro-3-amino-zinc tetraphenylporphyrin 4(515mg,0.70mmol) in 90% yield.
1H NMR(600MHz,CHCl3-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,NH2)。MS(MALDI-TOF):m/z calcd for C44H28ZnN6O2 736.21,found 736.34[M]+
The fourth step: preparation of 2, 3-diamino-tetraphenylporphyrin zinc 5
2-Nitro-3-amino-zinc tetraphenylporphyrin 4(400mg,0.54mmol) was dissolved in a mixed solution of dichloromethane and methanol (volume ratio 10: 1, 220 mL). N is a radical of2After bubbling for 20 minutes, 600mg of 10% palladium on carbon was added. System is N2Fully stirring for 10 minutes in the atmosphere, and slowly adding NaBH in batches after the system is uniformly dispersed4(532mg,14.4mmol), monitored by TLC until the zinc 2-nitro-3-amino-tetraphenylporphyrin 4 was completely consumed (ca. 2 h). After the reaction is finished, the reaction system is subjected to preliminary filtration by filling a kieselguhr flash column, and dichloromethane is used as an eluent (100mL) to obtain a crude product of 2, 3-diamino-tetraphenylporphyrin zinc 5. Because the beta-o-diaminoporphyrin is unstable in the air, the crude product of 2, 3-diamino-tetraphenylporphyrin zinc 5 is directly put into the next reaction without further purification and characterization.
The fifth step: preparation of porphyrin dimer 1 a.
To a solution of the crude 2, 3-diamino-tetraphenylporphyrin zinc 5 (0.54mmol) in dichloromethane under nitrogen protection was added diethyl oxalate (1.9mL,14.0mmol) and 20mL of methanol solution. The system was stirred at 60 ℃ for 6h followed by stirring at ambient temperature for 8 h. After the reaction is finished, the organic solvent is removed by reduced pressure distillation, column chromatography purification is carried out by taking dichloromethane/petroleum ether (volume is 2:3) as an eluent, and the reddish brown component with smaller polarity is collected. Further recrystallization from dichloromethane/methanol gave porphyrin dimer 1a (385mg,0.28mmol) in 40% yield.
1H NMR(600MHz,CHCl3-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 C88H52Zn2N10 1380.21,found 1381.80[M]+
Sixthly, preparing the porphyrin dimer graphene nonlinear composite material G-1a
Graphene (20mg) was dispersed in 30mL DMF for sufficient pre-sonication for approximately 3h to give a homogeneous suspension of graphene. Porphyrin dimer 1a (100mg) was added thereto and sonication was continued for 1 h. After the sonication was completed, the mixture was stirred at room temperature overnight. After the reaction is finished, filtering the solution by using a polytetrafluoroethylene membrane (0.22 micron), fully washing the obtained solid by using DMF (dimethyl formamide) and tetrahydrofuran, and drying the solid 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 carrying out sufficient ultrasound and centrifugation, and then directly carrying out Scanning Electron Microscope (SEM), total reflection infrared (FTIR), Raman spectroscopy (Raman) and photophysical research (steady-state absorption, fluorescence and z-scan research) on the supernatant. The photograph of the inset above G-1a in FIG. 1 shows pure graphene, porphyrin dimer 1a and porphyrin dimer graphene nanocomposite G-1a after being well dispersed in DMF and left to stand for three days. Different from graphene which is easy to precipitate, the porphyrin dimer graphene nanocomposite G-1a still shows relatively uniform suspension after three days, and preliminary evidence is provided for successfully attaching the porphyrin dimer 1a to the surface of graphene.
SEM testing provided the morphological information of pure graphene G and porphyrin dimer graphene nanocomposite G-1a, as shown in fig. 2a and 2 b. The non-functionalized graphene is very easy to agglomerate in an organic solvent and is not easy to disperse uniformly. After modification with porphyrin dimer 1a, the number of graphene layers was significantly reduced compared to fig. 2a, which is consistent with the results of the dispersion in DMF in fig. 1. To further gain elemental composition information, elemental mapping images of porphyrin dimer graphene nanocomposite G-1a are shown in fig. 2(c) to 2 (f). The distribution of N and Zn atoms is relatively small compared to the presence of C and O in large amounts, and the side indicates that porphyrin dimer functionalization on 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. Pure graphene spectrum except at 1682cm-1No significant signal was found outside of the central weak absorption, indicating that some carbonyl groups may remain in the commercially available graphene. The infrared spectrum of porphyrin dimer 1a shows the characteristic absorption of the porphyrin compound: 1220 and 1085cm-1Corresponding to the stretching vibration of pyrrole C-N at the center of porphyrin ring, 1645cm-1The absorption peak at (a) corresponds to C ═ N stretching vibration in the pyrazine ring between the two porphyrin monomers. Furthermore, is located at 1458cm-1And 660--1The peaks at (A) 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 combines the characteristic absorption peaks of the graphene and the porphyrin dimer 1a, and further confirms the successful attachment of the porphyrin dimer 1a on the surface of the graphene.
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 at 1300-1500cm-1The G peak is positioned at 1500--1. The presence of the D peak generally results from the disordered mode and sp of the surface lattice3Recombination of carbon atoms, and thus the degree of defect and disorder on the graphene surface, whereas the G peak is generally associated with sp2The compound carbon atoms are related to plane vibration derived from 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-1The central Raman shifts correspond to the respective C-C bonds v (C) on the porphyrin pyrrole ringαCm),v(CβCβ) V (pyrolean-half-ring), v (pyrolean-quartz-ring) and v (C)m-ph) of AgAnd B1gAnd (5) stretching and vibrating. Physics of physicsThe latter severely damages the integrity of the graphene crystal structure compared to the covalent bonding, so that the graphene composite material bonded by covalent bonding is usually accompanied by the strength ratio (I) of the D band and the G bandD/IG) Through pi-pi stacking interaction, the I of the porphyrin dimer graphene nanocomposite G-1a is obtainedD/IGThe ratio remains substantially unchanged, meaning that the graphene planar structure is not disrupted. Meanwhile, the characteristic displacement position of 1a on the Raman curve of the porphyrin dimer graphene nanocomposite G-1a is changed, strong resonance is generated between a single excitation state derived from porphyrin and graphene, and high electronic coupling between the graphene and the porphyrin dimer is proved.
Figure 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 typical broadband non-structural absorption, with the absorption intensity gradually decreasing from 300nm to 800 nm; ZnTPP exhibits the characteristic absorption bands of porphyrin monomers, for example a strong B (soret) band absorption at 423nm and a weaker Q band absorption at 559nm and 601 nm. In the case of porphyrin dimer 1a, B appears in the near ultraviolet and visible regions, respectivelyy(402nm)、Bx(501nm) and Qx(λmaxAt 600nm) three distinct absorption peaks. Porphyrin dimer 1a has a Q band (Q) of 1a compared to porphyrin monomer ZnTPPx) Slightly red-shifted, and obviously enhanced strength. The B band is split into two absorptions, ByAnd Bx. The change between ZnTPP and 1a is mainly due to the fact that two porphyrin monomers are connected through a conjugated pyrazine ring through a condensation reaction, and a pi-electron delocalization system is expanded. e.g. of the typegDegeneracy of the orbitals, exciton coupling between transition dipole moments and coulombic interactions, greatly perturb the electron distribution on the porphyrin ring, leading to changes in steady state absorption, similar to the results reported previously for fused porphyrin dimers. The electron absorption spectrum of the porphyrin dimer graphene nanocomposite G-1a shows the combination of the absorption spectra of the components, and meanwhile, compared with 1a, the absorption of a weaker low-energy Q band on the porphyrin dimer graphene nanocomposite G-1a occursA slight red shift indicates that component 1a produces an efficient electron-space interaction with graphene through pi-pi stacking.
The interaction between porphyrin dimer 1a and graphene can be further verified by fluorescence experiments. Materials with D-a structure are usually accompanied by efficient photo-energy and electron transfer processes. As shown in FIG. 4b, porphyrin dimer 1a exhibited a characteristic fluorescence peak at 635nm with a weaker shoulder at 710nm, when excited by 501nm light. Since graphene does not display a fluorescence signal, the fluorescence signal of porphyrin dimer graphene nanocomposite G-1a can be judged to be derived from porphyrin dimer 1a attached to the graphene surface. After the graphene is functionalized, porphyrin dimer 1a plays a role of an antenna and is excited to a singlet excited state, and due to the function of the graphene as an electron acceptor, energy on the porphyrin singlet excited state does not directly emit fluorescence to return to a ground state, but is transferred to the graphene at a lower energy level through energy transfer in a system, so that an obvious fluorescence quenching phenomenon (about 82%) is caused, and direct evidence is provided for effective photoinduced electron/energy transfer between a 1a component and the graphene.
Under 532nm and 12ns pulsed laser irradiation, the open-pore z-scan test was performed on the suspension of porphyrin monomer ZnTPP, porphyrin dimer 1a, graphene G and G-1a nanocomposite in DMF, and the results are shown in FIG. 5 (left). The method can fully explore the nonlinear optical performance of the precursor and the porphyrin dimer graphene nanocomposite G-1a, and particularly the difference of the reverse saturation absorption performance between porphyrin monomers and porphyrin dimer 1a connected by pyrazine rings. The linear transmittance of all samples was kept consistent (about 65%) by adjusting the concentration. Pure DMF had no detectable nonlinear optical properties, indicating that the contribution of solvent was negligible and the observed absorption was attributable to the solute. Furthermore, the effective nonlinear absorption coefficient (beta) can be further deduced by curve fitting the z-scanning dataeff). At the position where z is 0 (at the focal point of the lens), the normalized transmittances (T) of the graphene G, ZnTPP, the porphyrin dimer 1a and the porphyrin dimer graphene nanocomposite G-1a under 6.3 muj laser irradiation are respectively reduced from 100% to 75%,69%, 51% and 45%. The nonlinear absorption coefficients are 14.02(G), 16.18(ZnTPP), 21.36(1a) and 27.52(G-1a) cm/GW in sequence. The more interesting point is that from porphyrin monomer ZnTPP to porphyrin dimer 1a, the normalized transmittance decreased from 75% to 51%. Reported work shows that under ns laser conditions, the efficiency of reverse saturable absorption of the main nonlinear optical mechanism of porphyrin and derivatives thereof 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 saturable absorption efficiency. For the porphyrin monomer ZnTPP, the reverse saturable absorption dominated by excited state absorption is generally dominated by singlet excited state S1Excited state S transitioning to a higher energy level2、S3And triplet excited state T1Transition to T2、TnIs determined. 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 highly delocalized by pi-electrons into two absorptions ByBlend Bx. Wherein B isyThe energy is higher than the B band of ZnTPP, and the other energy is lower than the B band of ZnTPP. Different from the fused porphyrin dimer connected by the three wires, the porphyrin dimer 1a connected by the pyrazine ring has the service life of nanosecond level, and the service life of the magnitude order ensures that enough electrons on the first singlet excited state of porphyrin can continuously absorb photons to jump to a higher energy level, thereby showing stronger reverse saturation absorption performance and effective light restriction effect. In order to better evaluate the reverse saturable absorption capacity of porphyrin dimer 1a, the excited state absorption cross section (sigma) is obtained by further fitting calculationex) With the ground state absorption cross section (sigma)0) The ratio of (a) to (b). σ of ZnTPP and 1aex/σ0The ratios were 2.06 and 2.72, respectively, and the above mechanism concluded that the results were consistent. Normalized transmittance (T) of porphyrin dimer graphene nanocomposite G-1a at beam focus in all samples testedmin)The value is the lowest (45%) and the nonlinear coefficient is the largest (27.52cm/GW), indicating that the optical limiting effect is much stronger than that of pure graphene, 1a and porphyrin monomer ZnTPP, and is due to the synergistic effect of a plurality of mechanisms including nonlinear scattering of graphene, gamma-ray diffraction, and the like,The porphyrin dimer graphene nanocomposite G-1a has effective photoinduced electron energy transfer, and particularly has a greatly enhanced reverse saturable absorption effect of 1 a.
Example 2:
compared with the embodiment 1, the mixed acid solution is mostly the same except that in the embodiment, the mixed acid solution is prepared by mixing glacial acetic acid and acetic anhydride according to the volume ratio of 1:5, mixing the components; the molar ratio of tetraphenylporphyrin to copper acetate is 1: 2.5.
example 3:
compared with the embodiment 1, the mixed acid solution is mostly the same except that in the embodiment, the mixed acid solution is prepared by mixing glacial acetic acid and acetic anhydride according to the volume ratio of 1: 7, mixing; the molar ratio of tetraphenylporphyrin to copper acetate is 1: 3.
example 4:
compared to example 1, most of them are the same 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, of a nitrogen-containing gas; the volume ratio of toluene to ethanol was 250: 15.
Example 5:
compared to example 1, most of them are the same 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; the volume ratio of toluene to ethanol was 350: 15.
Example 6:
compared to example 1, most of them were the same except that in this example, the ratio of the addition amounts of copper 2-nitro-3-amino-tetraphenylporphyrin, dichloromethane, concentrated sulfuric acid, trifluoroacetic acid and zinc acetate was 1.0 mmol: 30mL, 30mL: 40mL of: 5 mmol. Example 7:
compared to example 1, most of them were the same except that in this example, the ratio of the addition amounts of copper 2-nitro-3-amino-tetraphenylporphyrin, dichloromethane, concentrated sulfuric acid, trifluoroacetic acid and zinc acetate was 1.2 mmol: 50mL, 50mL: 60mL of: 10 mmol.
Example 8:
compared to example 1, most of them were the same except that in this example, the ratio of the addition amounts of zinc 2-nitro-3-amino-tetraphenylporphyrin, palladium on carbon and sodium borohydride was 0.54 mmol: 500 mg: 10 mmol.
Example 9:
compared to example 1, most of them were the same except that in this example, the ratio of the addition amounts of zinc 2-nitro-3-amino-tetraphenylporphyrin, palladium on carbon and sodium borohydride was 0.54 mmol: 800 mg: 15 mmol.
Example 10:
compared to example 1, most of them are the same except that in this example, the molar ratio of zinc 2, 3-diamino-tetraphenylporphyrin to diethyl oxalate is 0.54: 10. here, the reaction process is specifically: the reaction is carried out for 7h at 50 ℃ and then for 7h at normal temperature.
Example 11:
compared to example 1, most of them are the same except that in this example, the molar ratio of zinc 2, 3-diamino-tetraphenylporphyrin to diethyl oxalate is 0.54: 15. here, the reaction process is specifically: the reaction is carried out for 5h at 70 ℃ and then for 9h at normal temperature.
Example 12:
compared with example 1, most of the components are the same, except that in the present example, the mass ratio of the graphene solid to the porphyrin dimer 1a may be about 1: 4.
Example 13:
compared with example 1, most of the components are the same, except that in the present example, the mass ratio of the graphene solid to the porphyrin dimer 1a may be about 1: 6.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, 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 embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure 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 a pi-pi stacking effect.
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 as claimed in claim 1 or 2, characterized by comprising the following steps:
(1) dissolving tetraphenylporphyrin in a dichloromethane solution, adding copper acetate dissolved in a mixed acid solution in advance, and stirring for reaction to obtain 2-nitro-copper tetraphenylporphyrin;
(2) reacting 2-nitro-copper tetraphenylporphyrin, 4-amino-4H-1, 2, 4-triazole and KOH in a mixed solution of toluene and ethanol, and separating a reaction product to obtain 2-nitro-3-amino-copper tetraphenylporphyrin;
(3) dissolving 2-nitro-3-amino-tetraphenylporphyrin copper in a dichloromethane solution, dropwise adding a mixture of concentrated sulfuric acid and trifluoroacetic acid, stirring and pouring ice water after rapid 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-zinc tetraphenylporphyrin in dichloromethane and methanol solution, adding palladium carbon, stirring uniformly, continuing adding sodium borohydride, reacting under the monitoring of thin-layer chromatography, and separating a reaction product to obtain 2, 3-zinc diaminoporphyrin;
(5) adding diethyl oxalate into a dichloromethane solution of 2, 3-diaminoporphyrin zinc, and reacting under the protection of nitrogen to obtain a porphyrin dimer 1 a;
(6) and ultrasonically dispersing the graphene solid in DMF (dimethyl formamide), adding porphyrin dimer 1a into the DMF, continuing to perform ultrasonic treatment, stirring the mixture at normal temperature for reaction, filtering and washing the reaction product to obtain a target product.
4. The preparation method of 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 the porphyrin dimer graphene nonlinear composite material according to claim 3, wherein 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 parts of; the volume ratio of the toluene to the ethanol is 250-350: 15.
6. The preparation method of the porphyrin dimer graphene nonlinear composite material according to claim 3, characterized in that 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 (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 ratio of the addition amounts of 2-nitro-3-amino-tetraphenylporphyrin zinc, palladium carbon and sodium borohydride is 0.54 mmol: (500-800) mg: (10-15) mmol.
8. The method for preparing the porphyrin dimer graphene nonlinear composite material as claimed in 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 specifically comprises the following steps: the reaction is carried out for 5-7 h at 50-70 ℃, and then for 7-9 h at normal temperature.
9. The preparation method of the porphyrin dimer graphene nonlinear composite material according to claim 3, characterized in that in the step (6), the graphene solid is fully subjected to ultrasonic treatment for 3 hours, and then porphyrin dimer 1a is added.
10. The application of the porphyrin dimer graphene nonlinear composite material as claimed in claim 1 or 2 in the nanosecond visible light field.
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