CN109776471B - Coumarin type organic third-order nonlinear optical material and preparation and application thereof - Google Patents
Coumarin type organic third-order nonlinear optical material and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a coumarin type organic third-order nonlinear optical material, which takes coumarin as a core group, and connects arylamine derivatives at the 6-position of the core group, wherein the arylamine derivatives comprise N, N-dimethylbenzene, triphenylamine and carbazole phenyl. The preparation mainly comprises the following steps: adding a coumarin derivative substituted by bromine at the 6-position, an arylamine derivative of pinacol borate and potassium carbonate into a solvent for dissolving; introducing nitrogen for 30min, adding a palladium tetratriphenylphosphine catalyst, heating to 80-100 ℃, reacting for 6-24 h at 1000-1200 r/min; extracting with dichloromethane and distilled water for several times, separating liquid, and drying; the obtained crude product is separated and purified. According to the invention, arylamine derivatives are introduced to the 6-position of coumarin to form a large D-Pi-A configuration, so that the nonlinear absorption coefficient and the two-photon absorption cross section value of coumarin molecules can be increased, and the coumarin compound can be applied to third-order nonlinear optical materials. The preparation method is simple, easy to operate, easy to obtain raw materials, low in cost and high in application value.
Description
Technical Field
The invention belongs to the field of organic third-order nonlinear optical materials, and particularly relates to a coumarin type organic third-order nonlinear optical material, a preparation method thereof and application thereof in the field of third-order nonlinear optical materials.
Background
The coumarin compound is a substance with aromatic odor, has a benzopyrone structure, is generally distributed in natural plants, and is a natural product with important function. Due to the particularity of the coumarin ring structure, the coumarin compound can be structurally modified at a plurality of positions, and the whole coumarin compound molecule can form a new electron conjugated structure according to the electron withdrawing or electron donating performance of the introduced modified group. In addition, a large conjugated system formed by C = C and C = O double bonds exists in coumarin molecules, and the lactone structure in the coumarin ring plays a role in enhancing the molecular rigidity, so that the coumarin compound can generate relatively strong fluorescence in a visible light range through the special internal structure, and the light quantum stability and the photoluminescence quantum yield of the coumarin compound are high. Therefore, the coumarin compound is generally used for producing functional materials with photoelectric response function. There are few applications of coumarin in third-order nonlinear optical materials.
The organic nonlinear optical material has the advantages of multiple relation between absorption wavelength and emission wavelength, quick response time, easy processing into high-quality optical devices and the like, and has great potential significance in information technology and industrial application. The two-photon absorption effect is a phenomenon of light exciting molecules under laser, and belongs to one of three-order nonlinear optical effects. The molecule absorbs two photons of the same or different frequencies simultaneously, producing a very high transient photon density. Organic compounds having a large two-photon cross-sectional value have been widely used in three-dimensional data storage, precision machining, microscopy, upconversion laser, photodynamic therapy, and the like, and have recently become a research hotspot of scientists. The coumarin material has good light, heat and chemical stability, light absorption characteristics, high fluorescence quantum yield, large molar absorption coefficient and electron delocalization, so that the coumarin material becomes a potential nonlinear precursor material. Therefore, the application of the coumarin type material in the aspect of third-order nonlinear optical materials is researched, and the coumarin type organic nonlinear optical material is developed, so that the coumarin type organic nonlinear optical material has practical significance.
Disclosure of Invention
The invention aims to provide a coumarin type organic third-order nonlinear optical material, and preparation and application thereof, so as to solve the problems in the prior art.
The coumarin type organic third-order nonlinear optical material takes coumarin as a core group, and an arylamine derivative is connected to the 6-position of the core group.
The substituent group is arylamine derivative, and arylamine is used as a dye with mild chemical property, low toxicity and environmental friendliness and is also commonly used for medicine synthesis. From the application point of view, the coumarin-arylamine system has a large potential.
At present, most of the substitution positions of coumarin types occur at 1 position, and the research of the invention finds that the substitution positions can effectively expand the conjugation range of a system when being at 6 positions, so that molecules form a large D-pi-A configuration, and the beta (nonlinear absorption coefficient) value of coumarin molecules is increased.
Further, the arylamine derivatives include N, N-dimethylbenzene and triphenylamine, and carbazole phenyl groups. Triphenylamine has more benzene rings and a larger conjugated system than N, N-dimethylaniline. Two benzene rings of carbazole phenyl are fixed by a carbon-carbon single bond, and can not rotate freely, so that the coplanarity is improved. The invention selects the three groups and researches the influence of small change of the structure on the two-photon absorption cross section value.
Further, the para position of the N, N-dimethylbenzene is connected with the 6 position of the coumarin group.
Further, the 4-position of the triphenylamine is connected with the 6-position of the coumarin group.
Further, the 4-position of the carbazole phenyl group is connected with the 6-position of the coumarin group.
The coumarin type organic third-order nonlinear optical material disclosed by the invention has a good two-photon absorption property, and the maximum absorption cross section value is as high as 103.6GM. The two-photon absorption cross-section values reported in the prior publications for very classical materials such as fluorescein, rhodamine B and rhodamine 6G are also only tens to a hundred and more GM.
The preparation of the coumarin organic third-order nonlinear optical material mainly comprises the following steps:
(1) Preparing a coumarin derivative brominated at the 6 th position;
(2) Through Suzuki coupling reaction, adding a coumarin derivative brominated at the 6-position, an arylamine derivative of pinacol borate and potassium carbonate into a solvent for dissolving;
(3) Introducing nitrogen for 30 minutes, adding a palladium tetratriphenylphosphine catalyst, heating to 80-100 ℃, reacting for 6-24 hours at 1000-1200 r/min;
(4) Extracting with dichloromethane and distilled water for multiple times, separating, and drying to obtain a crude product;
(4) Separating and purifying the obtained crude product by using dichloromethane/normal hexane as an eluent on a 200-300-mesh silica gel column.
The application of the coumarin organic third-order nonlinear optical material is applied to the third-order nonlinear optical material.
Further, the method comprises microscopy, precision machining, three-dimensional data storage, optical power limitation, up-conversion laser, photodynamic therapy and photoinduced release.
Compared with the prior art, the electron-donating group arylamine derivative is introduced to the 6-position of the coumarin, so that molecules form a large D-pi-A configuration, the nonlinear absorption coefficient and the two-photon absorption cross section value of the coumarin molecules are increased, the coumarin molecule has high two-photon absorption characteristics, and can be applied to three-order nonlinear optical materials, microscopy, precision machining, three-dimensional data storage, optical power limitation, upconversion laser, photodynamic therapy, photoinduced release and the like. The preparation method is simple, easy to operate, easy to obtain raw materials, low in cost and high in application value.
Drawings
FIG. 1 is a structural diagram of coumarin;
FIG. 2 is a structural diagram of Compound A obtained in example 1;
FIG. 3 is a structural diagram of Compound B obtained in example 2;
FIG. 4 is a structural diagram of Compound C obtained in example 3;
FIG. 5 is a schematic diagram of a Z-scan technique;
FIG. 6 is a graph showing the UV absorption spectrum and fluorescence spectrum of compounds A, B and C obtained in examples 1, 2 and 3, respectively, wherein fluorescence 1, fluorescence 2 and fluorescence 3 represent compounds A, B and C, respectively.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
The preparation method of the coumarin organic nonlinear optical material A mainly comprises the following steps:
(1) Firstly, preparing a coumarin derivative brominated at the 6 th position:
reacting coumarin and liquid bromine in a dichloromethane solution at room temperature for 48 hours, washing with a large amount of saturated sodium carbonate solution, extracting with dichloromethane, removing excessive solvent by using a rotary evaporator, recrystallizing by using methanol, filtering and drying to obtain yellow solid powder, and separating and purifying a crude product in a 200-300-mesh silica gel column by using dichloromethane-n-hexane (volume ratio of 2.
(2) And preparing para-N, N-dimethyl benzene substituted coumarin type derivatives:
the method mainly comprises the following steps: collecting the coumarin derivative (500mg, 2.2mmol) brominated at the 6-position, and introducing the N, N-dimethyl benzene derivative (618mg, 2.5mmol) and K of pinacol borate into the para-position 2 CO 3 (133 mg) was dissolved in a mixed solution of toluene and ethanol (3. Introducing nitrogen for 30min, adding 15mg of palladium tetratriphenylphosphine catalyst into the solvent, heating to 80 ℃ and 1000r/min, and reacting for 8 hours. After the reaction, the reaction mixture was cooled to room temperature, washed with a large amount of water, extracted with dichloromethane, and the excess solvent was removed by a rotary evaporator, and then 100mL of dichloromethane solution was added to dissolve the solid, washed with 40mL of distilled water, and separated. Removing residual water with anhydrous sodium sulfate, separating, and drying. The crude product was separated and purified on a 200-300 mesh silica gel column using dichloromethane-n-hexane (volume ratio 2.
The coumarin type organic nonlinear optical material compound A obtained by the preparation method has the yield of 60%.
Example 2
The preparation method of the coumarin organic nonlinear optical material B mainly comprises the following steps:
(1) The coumarin derivative brominated at the 6-position was prepared according to the method of example 1.
(2) And preparing a triphenylamine substituted coumarin type derivative:
the method mainly comprises the following steps: collecting the coumarin derivative (500mg, 2.2mmol) brominated at the 6-position, the derivative (927mg, 2.5mmol) obtained by introducing pinacol borate into the 4-position of triphenylamine, and K 2 CO 3 (133 mg), and the residue was dissolved in a mixed solution of toluene and ethanol (3. Introducing nitrogen for 30min, adding 15mg of palladium tetratriphenylphosphine catalyst into the solvent, heating to 80 ℃, and reacting for 8 hours at 1000 r/min. After the reaction, the reaction mixture was cooled to room temperature, washed with a large amount of water, extracted with dichloromethane, and the excess solvent was removed by a rotary evaporator, and then 100mL of dichloromethane solution was added to dissolve the solid, washed with 40mL of distilled water, and separated. Removing residual water with anhydrous sodium sulfate, separating, and drying. The crude product was isolated and purified on a 200-300 mesh silica gel column using dichloromethane-n-hexane (volume ratio 1.
The coumarin type organic nonlinear optical material compound B obtained by the preparation method has the yield of 62%.
Example 3
The preparation method of the coumarin-based organic nonlinear optical material C has a reaction formula as follows, and mainly comprises the following steps:
(1) The coumarin derivative brominated at the 6-position was prepared according to the method of example 1.
(2) And preparing a carbazole phenyl substituted coumarin type derivative:
the method mainly comprises the following steps: collecting 6-brominated coumarin derivative (500mg, 2.2mmol), 4-position boronic pinacol ester derivative (922mg, 2.5mmol) on carbazole phenyl and K 2 CO 3 (133 mg) was dissolved in a mixed solution of toluene and ethanol (3. Introducing nitrogen for 30min, adding 15mg of palladium tetratriphenylphosphine catalyst into the solvent, heating to 80 ℃, and reacting for 8 hours at 1000 r/min. After the reaction, the reaction mixture was cooled to room temperature, washed with a large amount of water, extracted with dichloromethane, and the excess solvent was removed by a rotary evaporator, and then 100mL of dichloromethane solution was added to dissolve the solid, washed with 40mL of distilled water, and separated. Removing residual water with anhydrous sodium sulfate, separating, and drying. The crude product was separated and purified on a 200-300 mesh silica gel column using dichloromethane-n-hexane (volume ratio 1.
The coumarin type organic nonlinear optical material compound C obtained by the preparation method has the yield of 41%.
Example 4
Coumarin is selected as a matrix, and N, N-dimethylbenzene, triphenylamine and carbazole phenyl are different substituents, so that the influence on the overall third-order nonlinear characteristic is avoided.
The coumarin-based organic nonlinear optical material compounds A, B and C prepared in examples 1, 2 and 3 are applied to a third-order nonlinear optical material, and a Z-scanning technology is used for measuring a third-order nonlinear absorption coefficient, a third-order nonlinear refractive index and a two-photon absorption cross section value of the third-order nonlinear optical material.
The principle of the Z-scan technique is shown in FIG. 5: the method comprises the following specific steps: laser emitted from a laser is attenuated by an attenuator A, a lens L focuses light beams, a beam splitter is arranged in front of the lens to divide the laser into two beams, one beam directly enters a detector D1 to measure transmitted light passing through a small hole, and the other beam enters another detector D2 to measure the change condition of input light after passing through a small hole with the center coinciding with an optical axis. Test sample compound a was fixed on a moving rack with a scale, and the sample position was read by the scale. Taking the focus as the origin of coordinates, moving the sample back and forth along the Z-axis from the focus, and as the sample moves in the light propagation direction (Z-direction) near the focus, due to the nonlinear effect of the medium, the light beam will diverge or converge, so the normalized transmittance T (D1/D2) will have a one-to-one correspondence with the sample position, and the normalized light beam transmittance can be expressed as:
wherein Z represents the distance between the sample and the focus center, Z 0 Represents the Rayleigh diffraction Length,/ 0 In order to be the peak power density,
is the effective length, L is the sample length, and β is the nonlinear absorption coefficient. The two-photon absorption coefficient was obtained by fitting experimentally measured transmittance data of formula (1), and then by the formula δ = h ω β/(2 π N) 0 ) Calculating the two-photon absorption cross-section value, wherein, h omega/(2 pi) is the energy of the excited photon, N 0 Is the number of molecules per cubic centimeter. Two-photon absorption cross-sectional value is generally expressed by GM, 1gm =1 × 10 -50 cm 4 s/photon。
TABLE 1 two-photon absorption coefficient and two-photon absorption section value of Compounds A, B and C
The three-order nonlinear optical properties of the compounds A, B and C are shown in Table 1, and the two-photon absorption coefficients and the absorption cross-section values are all better through Z scanning, particularly the two-photon absorption coefficient of the compound B reaches 7.84 multiplied by 10 -12 cm W -1 The two-photon absorption cross section value reaches 103.6GM. Has better two-photon absorption effect and is suitable for being applied to third-order nonlinear optical materials.
Ultraviolet absorption spectrum and fluorescence spectrum tests are carried out on the coumarin-based organic nonlinear optical material compounds A, B and C prepared in examples 1, 2 and 3, and rhodamine 6G aqueous solution (phi FL = 0.76) is used as a fluorescence standard. The test patterns are shown in FIG. 6, and the test data are shown in Table 2, which can result in emission wavelengths of 579, 570 and 510nm for compounds A-C, respectively.
TABLE 2 in CH 2 Cl 2 Ultraviolet absorption spectrum and fluorescence spectrum data of the compounds A, B and C measured in (1).
Cyclic voltammetry tests are carried out on the compounds A, B and C of the coumarin-based organic nonlinear optical materials prepared in the examples 1, 2 and 3, the redox potentials of the compounds A to C are measured through the cyclic voltammetry, and then the corresponding LUMO, HOMO and energy gap are calculated through the formula [ B ].
TABLE 3 correlation of the cyclic voltammetry measurements of the compounds A, B, C
[a]Measured in 0.05M tetrabutylammonium hexafluorophosphate in dichloromethane (vs. SCE) under argon. [ b ] a]E HOMO ＝-(4.4eV+E oxi(1) )。[c]The DFT is calculated under Gaussian 09 program based on rb3lyp/6-311g (d) module.
Through the analysis comparison, the compound B formed by substituting 6-position of coumarin by triphenylamine has the best third-order nonlinear property, and is far higher than other two structures. The molecule of the compound B structure is most beneficial to be applied to the third-order nonlinear optical material.
Exploration about the mechanism. The invention finds the experimental quantitative relation between the two-photon absorption cross section value and the molecular structure by fitting the service life of the excited charge separation state. The lifetimes of the coumarin-based organic nonlinear optical material compounds a, B, and C prepared in examples 1, 2, and 3 were experimentally fitted to obtain four lifetime values. Life span 1 (τ) 1 ) Is a high order excited singlet (S) n ) To the first excited singlet state (S) 1 ) The internal conversion process of (2); life 2 (τ) 2 ) Is the first excited singlet state (S) 1 ) Intramolecular charge transfer processes to the singlet excited state charge separation state (CS); life span 3 (τ) 3 ) Is a singlet excited charge separated state (CS) to a triplet excited charge separated state (CS) 3 ) The inter-system crossing process of (2); life span 4 (τ) 4 ) Is a triplet excited charge separated state (CS) 3 ) To the ground state (S) 0 ) The outer conversion process of (1). Where lifetime 3 represents the lifetime of the singlet excited charge separation state. The research of the invention finds that the service life can be used as the experimental criterion of the quantitative relation between the two-photon absorption cross section value and the molecular structure. Obtained by comparison, lifetime 3 (. Tau.) 3 ) The size sequence of is C<A<B; the two-photon absorption cross-section value has the sequence of C<A<B. The two-photon absorption cross-sectional value is linear with the hole-electron center distance (Δ r) of the excited state, and a larger Δ r means that the longer the center distance between the hole and the electron of the excited state, the longer the time for recombination of the hole and the electron, and the longer the lifetime of the charge separated state of the excited state.
TABLE 4 Life-time fit of Compounds A, B, C
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention. Therefore, the present invention is not limited to the specific embodiments described above.
Claims (4)
1. The coumarin type organic third-order nonlinear optical material is characterized in that coumarin is used as a core group, and an arylamine derivative is connected to the 6-position of the core group, wherein the formula of the compound is as follows:
the arylamine derivative includes a carbazole phenyl group; and the 4-position of the carbazole phenyl group is connected with the 6-position of the coumarin group.
2. The method for preparing the coumarin organic third-order nonlinear optical material as described in claim 1, which mainly comprises the following steps:
(1) Preparing a coumarin derivative brominated at the 6-position, wherein the coumarin derivative is represented by the following formula:
(2) Through Suzuki coupling reaction, adding a coumarin derivative brominated at the 6-position, an arylamine derivative of pinacol borate and potassium carbonate into a solvent for dissolving, wherein the arylamine derivative of pinacol borate is shown as the following formula:
(3) Introducing nitrogen for 30 minutes, adding a palladium tetratriphenylphosphine catalyst, heating to 80-100 ℃, reacting for 6-24 hours at 1000-1200 r/min;
(4) Extracting with dichloromethane and distilled water for multiple times, separating liquid, and drying to obtain a crude product;
(5) Separating and purifying the obtained crude product by using dichloromethane/normal hexane as an eluent on a 200-300-mesh silica gel column.
3. Use of the coumarin-based organic third-order nonlinear optical material of claim 1 in a third-order nonlinear optical material.
4. The use of claim 3, comprising microscopy, precision machining, three-dimensional data storage, optical power limiting, upconversion laser, and photoreleasing.
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| "6-Arylcoumarins as Novel Nonsteroidal Type Progesterone Antagonists: An Example with Receptor-Binding-Dependent Fluorescence";Sakai, Haruka，et al.;《JOURNAL OF MEDICINAL CHEMISTRY》;20110914;第54卷(第20期);第7058页Table1，第7057页Scheme 1,Scheme 2，第7061页Synthesis of 8. * |
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