CN113045598B - Oligothiophene functionalized ortho-carborane derivatives, and synthesis method and optical amplitude limiting application thereof - Google Patents
Oligothiophene functionalized ortho-carborane derivatives, and synthesis method and optical amplitude limiting application thereof Download PDFInfo
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Abstract
The invention discloses oligothiophene functionalized orthocarborane derivatives, a synthesis method and an optical limiting application thereof, and belongs to the technical field of organic luminescent materials. The oligothiophene functionalized ortho carborane derivatives have the advantages of simple synthesis method, high yield, excellent properties of both oligothiophene and carborane, rich assembly behaviors, overcome the defect of fluorescence attenuation or quenching caused by the aggregation of oligothiophene molecules, typical aggregation-induced luminescence property, large Stokes shift, strong chemical stability and processability, strong two-photon three-order nonlinear optical response, wide application prospect and the like, and can be used in the fields of optical amplitude limiting, organic luminescence, bioluminescence probes, chemical sensing and the like.
Description
Technical Field
The invention belongs to the technical field of organic luminescent materials, and particularly relates to oligothiophene functionalized orthocarborane derivatives, a synthetic method thereof and application of light amplitude limiting characteristics.
Background
The focus of people is brought about by the fact that an Aggregation Induced Emission (AIE) material has unique photoluminescence enhancement behaviors in a solid state and a thin film state, the problem of fluorescence clustering quenching encountered by the traditional organic fluorescent molecules is solved, and the novel molecular structure design preparation and function development are still hot spots of current scientific research work. Oligothiophenes are pi conjugated compounds of an electron-rich system and have excellent photoelectric properties; as the degree of pi-electron conjugation increases, the fluorescence emission wavelength of oligothiophenes is red-shifted, and Stokes (Stokes) shifts increase. It is worth noting that the oligothiophene derivative has a definite structure, is easy for functional modification and molecular regulation, and is a model molecule for polythiophene research. Because oligothiophene contains active S heteroatom, lower highest occupied orbital (HOMO) energy and wider energy gap, the oligothiophene is easy to react with oxygen and water in the air under the irradiation of ultraviolet light or visible light, the use stability of a device or a sensor prepared on the basis of the oligothiophene is influenced, and the practical application of the material is limited. One of the effective ways to improve the thermochemical and photochemical stability of the oligothiophene and its derivatives is to modify the terminal electron-donating or electron-withdrawing group of the oligothiophene, and this structural modification is helpful to adjust the energy level structure and the electron cloud density distribution of the oligothiophene and its derivatives, thereby improving the photoelectric properties and the chemical stability thereof. On the other hand, as an important class of polyhedral heteroborane derivatives, carborane and derivatives thereof are receiving attention from more and more researchers due to their physicochemical characteristics, such as high chemical/thermal stability, abundant functionalization modes, unique stereoaromaticity, and special electronic structures, and have been widely used in the fields of chemistry, biology, materials, and the like. Literature investigations have shown that AIE properties are prone to occur when conjugated luminescent moieties are directly coupled to the C-C position of a vicinal carborane backbone. The reason may be that the electron-withdrawing effect of the carborane transfers charges in a conjugated segment of the carborane to the carborane through a C-C bond, so that a charge transfer state is formed, and the intrinsic conjugated segment of the carborane disappears, however, C-C bond vibration is easy to occur in a solution, so that energy is dissipated in a non-radiation form, and the phenomenon that fluorescence emission is quenched is shown, and when the carborane is gathered in a solid state, a crystalline state or a solution, the C-C bond vibration is weakened or blocked, and the fluorescence emission is recovered. Particularly, in an excited state, electrons of the o-carborane are mainly delocalized on the boron side of a cage due to the special boron-carbon structure of the o-carborane, and therefore the o-carborane has a strong electron withdrawing characteristic. Therefore, most of the adjacent carborane C-C derived conjugated molecule systems have obvious push-pull electronic structure characteristics, so that excited state processes such as local excited state (LE state), charge separation state (CT state) and Excimer state (Excimer state) formation are shown.
In a word, the carborane has the characteristics of unique three-dimensional cage-shaped rigid structure, aromaticity, high thermal stability and the like, is easy to functionally modify, can increase the conjugation degree of a target system, regulates and controls the monomolecular and aggregation-state photoelectric properties of the obtained target product, and can be directly coupled with oligothiophene groups through conjugated bonds on the basis of the ortho carborane to obtain fluorescent active molecules or molecular systems with specific performance, so that the derivatives have special photophysical properties and application.
Disclosure of Invention
The invention aims to provide oligothiophene functionalized orthocarborane derivatives, and provides a synthetic method and application thereof.
The structural formula of the oligothiophene functionalized orthocarborane derivative is shown as follows:
in the formula, the & lt + & gt represents BH, and R represents any structural unit of hydrogen, thiophene, benzene, naphthalene, anthracene, pyrene, dithiophene and trithiophene.
When R in the structural formula represents hydrogen, the method for synthesizing the oligothiophene functionalized orthocarborane derivative comprises the following steps:
1. synthesis of Compound 1
Adding 5-bromo-2, 2 ', 5 ', 2 ' -trithiophene, palladium tetrakis (triphenylphosphine), cuprous iodide and trimethylsilyl acetylene into a mixed solvent of triethylamine and tetrahydrofuran, heating to 60-90 ℃ under the protection of nitrogen, stirring for reacting for 8-12 hours, cooling to room temperature, spin-drying, separating, purifying and drying by using column chromatography to obtain a bright yellow solid compound 1.
2. Synthesis of Compound 2
Adding the compound 1 and potassium carbonate into a mixed solvent of tetrahydrofuran and methanol, stirring for 1-3 hours at room temperature, spin-drying, separating and purifying by column chromatography, and drying to obtain a yellow solid compound 2.
3. Synthesis of oligothiophene functionalized orthocarborane derivatives
Adding decaborane into a mixed solvent of anhydrous toluene and N, N-dimethylaniline, stirring for 20-40 minutes at room temperature under the protection of nitrogen, adding a compound 2, heating to 100-120 ℃, stirring for 8-10 hours, cooling to room temperature, spin-drying, and separating and purifying by column chromatography to obtain the oligothiophene functionalized ortho-carborane derivative.
In the step 1, the mol ratio of 5-bromo-2, 2 ': 5 ', 2 ' -trithiophene, tetrakis (triphenylphosphine) palladium, cuprous iodide and trimethylsilyl acetylene is preferably 1: 0.02-0.05: 1-1.2.
In the step 2, the molar ratio of the compound 1 to the potassium carbonate is preferably 1: 2-5.
In the step 3, the molar ratio of decaborane to the compound 2 is preferably 1:4 to 5.
When R in the structural formula represents any structural unit of thiophene, benzene, naphthalene, anthracene, pyrene, dithiophene and trithiophene, the synthetic method of the oligothiophene functionalized orthocarborane derivative comprises the following steps:
1. synthesis of Compound 3
Placing the compound 2, tetrakis (triphenylphosphine) palladium, cuprous iodide, bromide R-Br, triethylamine and tetrahydrofuran in a pressure-resistant tube, heating to 60-90 ℃ under the protection of nitrogen, stirring for reacting for 8-12 hours, cooling to room temperature, spin-drying, separating, purifying and drying by using column chromatography to obtain a yellow solid compound 3.
The above-mentioned bromides R-Br are
Any one of them.
2. Synthesis of oligothiophene functionalized orthocarborane derivatives
Adding decaborane into a mixed solvent of anhydrous toluene and N, N-dimethylaniline, stirring for 20-40 minutes at room temperature under the protection of nitrogen, adding a compound 3, heating to 100-120 ℃, stirring for 8-10 hours, cooling to room temperature, spin-drying, and separating and purifying by column chromatography to obtain the oligothiophene functionalized ortho-carborane derivative.
In the step 1, the molar ratio of the compound 2 to tetrakis (triphenylphosphine) palladium, cuprous iodide, bromide R-Br and triethylamine is preferably 1: 0.02-0.05: 1-1.2.
In the step 2, the molar ratio of decaborane to the compound 3 is preferably 1:4 to 5.
The oligothiophene functionalized orthocarborane derivative has strong two-photon three-order nonlinear optical response, and can be used as an optical limiting material to be applied to the field of laser protection.
The invention has the following beneficial effects:
1. the invention synthesizes oligothiophene functionalized orthocarborane derivatives, which have the excellent properties of both oligothiophene and carborane and abundant assembly behaviors. The strong electron-withdrawing ability of the ortho carborane and the electron-donating ability of the oligothiophene derivative group form a donor-acceptor structure, so that the strong two-photon three-order nonlinear optical response is shown while the charge transfer is facilitated, and the ortho-carborane can be used as a light amplitude limiting material to be applied to the field of laser protection.
2. The oligothiophene functionalized orthocarborane derivative overcomes the defect of fluorescence weakening or quenching caused by aggregation of oligothiophene molecules, has a typical AIE luminescence characteristic in a solid state, has large Stokes shift and high fluorescence quantum yield, and obtains a high-efficiency thin-film or solid luminescent material.
3. Compared with oligothiophene, the oligothiophene functionalized orthocarborane derivative has better photochemical stability, the introduction of the orthocarborane effectively enhances the solubility and the processability of the derivative, and is expected to play an important role in designing and synthesizing a novel optical limiting material with excellent comprehensive performance and in application of fluorescent materials.
Drawings
FIG. 1 is a diagram of oligothiophene functionalized orthocarborane derivative 4-1 prepared in example 1 1 H NMR spectrum.
FIG. 2 is the oligothiophene functionalized orthocarborane derivative 4-1 prepared in example 1 13 C NMR spectrum.
FIG. 3 shows example 1Preparation of oligothiophene functionalized orthocarborane derivative 4-1 11 B NMR spectrum.
FIG. 4 is a high resolution mass spectrum of oligothiophene functionalized orthocarborane derivative 4-1 prepared in example 1.
FIG. 5 is a UV-Vis spectrum of oligothiophene functionalized orthocarborane derivative 4-1 prepared in example 1 in tetrahydrofuran.
FIG. 6 is a graph of the fluorescence emission spectrum of oligothiophene functionalized orthocarborane derivative 4-1 prepared in example 1 as a function of the volume ratio of tetrahydrofuran to water.
FIG. 7 is a graph showing the relationship between the fluorescence intensity at 601nm and the volume ratio of tetrahydrofuran to water in the fluorescence emission spectrum of the oligothiophene functionalized orthocarborane derivative 4-1 prepared in example 1.
FIG. 8 is a graph of the nonlinear absorption characteristics and the variation of excitation light energy of oligothiophene functionalized orthocarborane derivative 4-1 prepared in example 1 under the action of laser light of 200fs, 10kHz and 650 nm.
FIG. 9 is a diagram of oligothiophene functionalized orthocarborane derivatives 4-2 prepared in example 2 1 H NMR spectrum.
FIG. 10 is a diagram of oligothiophene functionalized orthocarborane derivatives 4-2 prepared in example 2 13 C NMR spectrum.
FIG. 11 is a diagram of oligothiophene functionalized orthocarborane derivatives 4-2 prepared in example 2 11 B NMR spectrum.
FIG. 12 is a high resolution mass spectrum of oligothiophene functionalized orthocarborane derivative 4-2 prepared in example 2.
FIG. 13 is a UV-Vis spectrum of oligothiophene functionalized orthocarborane derivative 4-2 prepared in example 2 in tetrahydrofuran.
FIG. 14 is a graph of fluorescence emission spectrum of oligothiophene functionalized orthocarborane derivative 4-2 prepared in example 2 as a function of tetrahydrofuran-water volume ratio.
FIG. 15 is a graph of fluorescence intensity at 693nm of fluorescence emission spectrum of oligothiophene functionalized orthocarborane derivative 4-1 prepared in example 1 as a function of tetrahydrofuran-water volume ratio.
FIG. 16 is a graph showing the nonlinear absorption characteristics and the energy variation of excitation light of oligothiophene functionalized orthocarborane derivative 4-2 prepared in example 1 under the action of laser beams at 200fs, 10kHz and 650 nm.
FIG. 17 is a graph showing two-photon absorption characteristics of oligothiophene functionalized orthocarborane derivatives 4-1 and 4-2 prepared in examples in the range of 620nm to 850 nm.
FIG. 18 is a graph of input laser energy and output laser energy of oligothiophene functionalized vicinal carborane derivatives 4-1 and 4-2 prepared in the examples under the action of 200fs, 10kHz and 650nm lasers.
FIG. 19 is a graph showing the relationship between the transmittance and the input laser energy of oligothiophene functionalized orthocarborane derivatives 4-1 and 4-2 prepared in the examples under the action of laser beams of 200fs, 10kHz and 650 nm.
Detailed Description
The invention is described in more detail below with reference to the figures and examples, but the scope of the invention is not limited to these examples.
Example 1
1. Synthesis of Compound 1
Under the protection of nitrogen, 0.654g (2.0mmol) of 5-bromo-2, 2 ': 5', 2 "-trithiophene (3T-Br), 46.2mg (0.04mmol) of tetrakis (triphenylphosphine) palladium, 7.6mg (0.04mmol) of cuprous iodide and 0.236g (2.4mmol) of trimethylsilylacetylene were weighed into a pressure tube, and 20mL of triethylamine and 40mL of tetrahydrofuran were sequentially added into the pressure tube, heated to 60 ℃, stirred for reaction for 12 hours, cooled to room temperature, spin-dried, subjected to column chromatography using a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:20 as an eluent, and dried to obtain 0.42g of bright yellow solid compound 1 with a yield of about 62%. The reaction equation is as follows:
the structural characterization data for compound 1 obtained are: 1 H NMR(CDCl 3 ,400MHz)δ:7.23(dd,J＝5.1,1.1Hz,1H),7.17(dd,J＝3.6,1.1Hz,1H),7.12(d,J＝3.8Hz,1H),7.07(s,2H),7.02(dd,J＝5.1,3.6Hz,1H),6.99(d,J＝3.8Hz,1H),0.29-0.22(m,9H)； 13 C NMR(CDCl 3 ,100MHz,ppm)δ：138.69,137.09,137.03,135.52,133.67,128.08,125.00,124.91,124.54,124.09,123.31,122.03,100.40,97.52,76.85；HRMS(APCI,m/z):[M+H] + theoretical value C 17 H 16 S 3 Si, 345.0245; experimental value 345.0256.
2. Synthesis of Compound 2
0.34g (1.0mmol) of compound 1 and 0.28g (2.0mmol) of potassium carbonate are weighed into a 50mL round-bottomed flask, 30mL of tetrahydrofuran and 10mL of methanol are added, stirred at room temperature for 2 hours, spun-dried, and subjected to column chromatography using n-hexane as an eluent to obtain 0.24g of compound 2 as a yellow solid in about 90% yield. The reaction equation is as follows:
3. synthesis of oligothiophene functionalized orthocarborane derivative 4-1
Under nitrogen protection, 0.244g (2.0mmol) decaborane (B) was weighed out 10 H 14 ) Adding 42mL of anhydrous toluene and 0.13mL of N, N-dimethylaniline into a pressure tube, stirring at room temperature for 40 minutes, adding 2.179g (8.0mmol) of compound 2, heating to 100 ℃, stirring for 8 hours, cooling to room temperature, spin-drying, and performing column chromatography by using a mixture of dichloromethane and petroleum ether in a volume ratio of 1:25 as eluent to obtain yellow solid oligothiophene functionalized orthocarborane derivative 4-1 with the yield of about 70%. The reaction equation is as follows:
the structural characterization data of the oligothiophene functionalized orthocarborane derivative 4-1 are as follows: 1 H NMR(400MHz,CDCl 3 )δ:7.24(dd,J＝5.1,1.1Hz,1H),7.17(dd,J＝3.6,1.1Hz,1H),7.08(d,J＝3.9Hz,1H),7.06(q,J＝3.8Hz,1H),7.02(dd,J＝5.1,3.6Hz,2H),6.91(d,J＝3.9Hz,1H),3.84(s,1H),3.06-1.55(m,10H) (see FIG. 1); 13 C NMR(151MHz,CDCl 3 ppm) δ 139.67,137.74,136.60,134.79,134.14,130.70,128.01,125.42,125.06,124.40,124.18,123.14,71.92,63.31ppm (see fig. 2); 11 B NMR(192MHz,CDCl 3 ppm) delta-0.91, -1.69, -4.16, -4.90, -8.86, -9.63, -10.49, -10.86, -12.00, -12.93 (see FIG. 3); HRMS (APCI-Orbitrap) M/z: [ M + H] + Theoretical value C 14 H 18 B 10 S 3 391.1642, experimental value 391.1654 (see FIG. 4); the crystal belongs to a triclinic system, P-1 space group, Z is 8, unit cell parameter
The X-ray density is 1.334mg/m 3 (Single crystal data are shown in Table 1).
As can be seen from FIG. 5, the maximum absorption wavelength of the oligothiophene functionalized orthocarborane derivative 4-1 in tetrahydrofuran is 367nm, and the influence of the polarity of the solvent is small; its molar absorption coefficient in tetrahydrofuran solution is as high as 2.66X 10 4 M -1 ·cm -1 . Under 365nm ultraviolet irradiation, the solid state emits red fluorescence, and the absolute fluorescence quantum yield of the solid state is 16.7%. FIG. 6 and FIG. 7 show that the oligothiophene functionalized orthocarborane derivative 4-1 has AIE characteristics, the fluorescence emission spectrum of the oligothiophene functionalized orthocarborane derivative is obviously changed along with the gradual increase of the water volume ratio in the tetrahydrofuran-water mixed solution, and the fluorescence intensity at 601nm is gradually enhanced along with the gradual increase of the water volume ratio in the tetrahydrofuran-water mixed solution. From FIG. 8, it can be seen that the spectrum exhibits a valley shape, and the normalized nonlinear transmittance gradually decreases as the intensity of the excitation light increases from 5.21mW to 18.01mW, indicating that the prepared derivative 4-1 has a stronger nonlinear absorption property.
Example 2
1. Synthesis of Compound 3-1
Under the protection of nitrogen, 0.27g (1.0mmol) of the compound 2, 23.1mg (0.02mmol) of tetrakis (triphenylphosphine) palladium, 3.8mg (0.02mmol) of cuprous iodide and 0.391g (1.2mmol) of 5-bromo-2, 2 ': 5', 2 "-trithiophene (3T-Br) are weighed in a pressure-resistant tube, 20mL of triethylamine and 40mL of tetrahydrofuran are sequentially added into the pressure-resistant tube, the mixture is heated to 90 ℃, stirred and reacted for 12 hours, cooled to room temperature and dried by spinning, and the mixture of dichloromethane and petroleum ether with the volume ratio of 2:1 is used as eluent to carry out column chromatography separation and drying, so that the yellow solid compound 3-1 is obtained. The reaction equation is as follows:
2. synthesis of oligothiophene functionalized orthocarborane derivative 4-2
Under nitrogen protection, 0.244g (2.0mmol) decaborane (B) was weighed out 10 H 14 ) Adding 42mL of anhydrous toluene and 0.13mL of N, N-dimethylaniline into a pressure-resistant tube, stirring at room temperature for 40 minutes, adding 4.15g (8.0mmol) of the compound 3-1, heating to 100 ℃, stirring for 8 hours, cooling to room temperature, spin-drying, and performing column chromatography separation by using a mixture of dichloromethane and petroleum ether with a volume ratio of 1:30 as an eluent to obtain a yellow solid oligothiophene functionalized orthocarborane derivative 4-2 with a yield of about 35%. The reaction equation is as follows:
the structural characterization data of the oligothiophene functionalized orthocarborane derivative 4-2 are as follows: 1 H NMR(600MHz,CDCl 3 ppm) δ 7.22(d, J ═ 4.9Hz,1H),7.14(d, J ═ 3.4Hz,1H),7.10(d, J ═ 3.9Hz,1H),7.03(q, J ═ 3.8Hz,2H),7.01-6.99(m,1H),6.87(d, J ═ 3.9Hz,1H),2.26(dd, J ═ 100.3,63.9Hz,5H) (see fig. 9); 13 C NMR(150MHz,THF-d 8 ppm) delta 141.93,138.28,136.84,134.57,134.47,132.74,128.34,126.27,125.63,124.81,124.59,123.89 (see FIG. 10); 11 b NMR (192MHz, THF, ppm): delta-2.59, -3.26, -9.43, -10.65, -11.37 (see FIG. 11); HRMS (APCI-Orbitrap) M/z: [ M + H] + Theoretical value C 26 H 24 B 10 S 6 637.1290, respectively; experimental value 637.1293 (see fig. 12); the crystal belongs to monoclinic system, P2 1/n Space group, Z-4, unit cell parameter
And the X-ray density is 1.409mg/m 3 (Single crystal data are shown in Table 1).
As can be seen from FIG. 13, the maximum absorption wavelength of the oligothiophene functionalized orthocarborane derivative 4-2 in tetrahydrofuran is 370nm, and the influence of the polarity of the solvent is small; its molar absorptivity in tetrahydrofuran solution is up to 3.67X 10 4 M -1 ·cm -1 . Under 365nm ultraviolet irradiation, the solid state emits red fluorescence, and the solid state absolute fluorescence quantum yield is 21.8%. FIG. 14 and FIG. 15 show that the oligothiophene functionalized orthocarborane derivative 4-2 has AIE characteristics, the fluorescence emission spectrum of the oligothiophene functionalized orthocarborane derivative is obviously changed along with the gradual increase of the water volume ratio in the tetrahydrofuran-water mixed solution, and the fluorescence intensity at 693nm is gradually enhanced along with the gradual increase of the water volume ratio in the tetrahydrofuran-water mixed solution. From FIG. 16, it can be found that the spectrum exhibited a valley shape, and the normalized nonlinear transmittance was gradually decreased as the intensity of the excitation light was increased from 7.75mW to 19.91mW, indicating that the prepared derivative 4-2 had a stronger nonlinear absorption property.
Example 3
Oligothiophene functionalized orthocarborane derivatives obtained in example 1 and example 2 are used as optical limiting materials
The oligothiophene functionalized orthocarborane derivatives 4-1 and 4-2 are respectively prepared into a concentration of 1.0 multiplied by 10 by THF - 2 And (3) carrying out ultrasonic treatment on the solution in mol/L for 3-5 minutes, wherein the color of the solution is yellow.
FIG. 17 shows the two-photon absorption cross-sectional values of the oligothiophene functionalized vicinal carborane derivatives 4-1 and 4-2 in the range of 620nm to 850nm, from which we can see that the maximum two-photon absorption cross-sectional value of the oligothiophene functionalized vicinal carborane derivative 4-1 is 104GM at 650nm, and the nonlinear absorption coefficient is calculated to be about 2.0 × 10 -2 cm/GW; the maximum two-photon absorption cross-section value of the oligothiophene functionalized ortho-carborane derivative 4-2 at 650nm is 118GM, and the nonlinear absorption coefficient can be calculated to be about 2.3 multiplied by 10 -2 cm/GW; indicating that the oligothiophene of the present invention is functionalizedThe carborane derivative has stronger two-photon nonlinear absorption characteristic.
FIGS. 18 and 19 show the optical amplitude limiting performance of THF solutions of oligothiophene functionalized ortho-carborane derivatives 4-1 and 4-2 under the action of 650nm laser, and from the graphs, we can find that with the increasing intensity of incident laser, the energy of output light no longer follows the linear Langerbil law, but the increasing amplitude of the output laser intensity is continuously reduced, and the phenomenon shows that the oligothiophene functionalized ortho-carborane derivatives have excellent optical amplitude limiting effect.
TABLE 1
Claims (5)
1. A method for synthesizing oligothiophene functionalized orthocarborane derivatives has the following structural formula:
in the formula, the R represents any structural unit of thiophene, benzene, naphthalene, anthracene, pyrene, dithiophene and trithiophene, and the method is characterized by comprising the following steps:
(1) synthesis of Compound 1
Adding 5-bromo-2, 2 ', 5', 2 '' -trithiophene, tetrakis (triphenylphosphine) palladium, cuprous iodide and trimethylsilyl acetylene into a mixed solvent of triethylamine and tetrahydrofuran, heating to 60-90 ℃ under the protection of nitrogen, stirring for reacting for 8-12 hours, cooling to room temperature, spin-drying, separating and purifying by column chromatography, and drying to obtain a bright yellow solid compound 1;
compound 1
(2) Synthesis of Compound 2
Adding the compound 1 and potassium carbonate into a mixed solvent of tetrahydrofuran and methanol, stirring for 1-3 hours at room temperature, spin-drying, separating and purifying by column chromatography, and drying to obtain a yellow solid compound 2;
compound 2
(3) Synthesis of Compound 3
Placing the compound 2, palladium tetrakis (triphenylphosphine), cuprous iodide, bromide R-Br, triethylamine and tetrahydrofuran in a pressure-resistant tube, heating to 60-90 ℃ under the protection of nitrogen, stirring for reacting for 8-12 hours, cooling to room temperature, spin-drying, separating and purifying by column chromatography, and drying to obtain a yellow solid compound 3;
compound 3
The above-mentioned bromides R-Br are
、
、
、
、
、
、
Any one of them;
(4) synthesis of oligothiophene functionalized orthocarborane derivatives
Decaborane is added to anhydrous toluene andN,Nstirring the mixed solvent of-dimethylaniline for 20-40 minutes at room temperature under the protection of nitrogen, adding a compound 3, heating to 100-120 ℃, stirring for 8-10 hours, cooling to room temperature, spin-drying, and separating and purifying by column chromatography to obtain the oligothiophene functionalized ortho-carborane derivative.
2. The process for the synthesis of oligothiophene functionalized orthocarborane derivatives according to claim 1, wherein: in the step (1), the molar ratio of the 5-bromo-2, 2 ', 5', 2 '' -trithiophene, tetrakis (triphenylphosphine) palladium, cuprous iodide and trimethylsilyl acetylene is 1: 0.02-0.05: 1-1.2.
3. The process for the synthesis of oligothiophene functionalized orthocarborane derivatives according to claim 1, wherein: in the step (2), the molar ratio of the compound 1 to the potassium carbonate is 1: 2-5.
4. The process for the synthesis of oligothiophene functionalized orthocarborane derivatives according to claim 1, wherein: in the step (3), the molar ratio of the compound 2, the palladium tetrakis (triphenylphosphine), the cuprous iodide, the bromide R-Br and the triethylamine is 1: 0.02-0.05: 1-1.2.
5. The process for the synthesis of oligothiophene functionalized orthocarborane derivatives according to claim 1, wherein: in the step (4), the molar ratio of the decaborane to the compound 3 is 1: 4-5.
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