CN114853962A - Preparation method of near-infrared two-region beta-diketone macromolecular rare earth complex with AIE activity - Google Patents
Preparation method of near-infrared two-region beta-diketone macromolecular rare earth complex with AIE activity Download PDFInfo
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Abstract
The invention discloses a preparation method of near-infrared two-region beta-diketone macromolecular rare earth complex with AIE activity, which adopts RAFT active free radical polymerization technology to firstly synthesize polytetrastyrene PTPE with trithioester at the end, uses the polytetrastyrene PTPE as RAFT macromolecular chain transfer agent to initiate polymerization of beta-diketone monomer containing vinyl, and finally obtains block polymer (PTPE-g-beta-DK) containing tetraphenstyrene unit and beta-diketone unit, and uses the block polymer as a first ligand, triphenylphosphine oxide as a second ligand and Nd 3+ And (3) carrying out coordination to obtain the near-infrared two-region luminescent polymer lanthanide series AIE fluorescent material (PTPE-g-beta-DK-Nd). TEM and DLS test results show that PTPE-g-beta-DK-Nd is agglomerated particles, has a linear structure of a high polymer material, and the typical particle size is 80-180 nm. PTPE-g-beta-DK-Nd in the near infrared two-region range of 1060nm and 133Fluorescence emission exists at 0nm, and the probe can be used as a potential near-infrared two-region biological fluorescent probe.
Description
Technical Field
The invention relates to a preparation method of a near-infrared two-region beta-diketone macromolecular rare earth complex with AIE activity, belonging to the technical field of fluorescent material preparation.
Background
In recent years, ratiometric fluorescence methods based on the antenna effect have attracted considerable attention. Ln 3+ Has a small molar absorption coefficient and a weak light absorption capacity. In addition, 4f-4f transition is hindered, all of which result in low luminous efficiency. Some chromophore compounds with strong absorption will transfer the absorbed energy to Ln 3+ This causes an antenna effect, Ln 3+ And (3) light emitting and sensitizing. Beta-diketone compounds and porphyrin derivatives are common antenna ligands. Furthermore, functional groups such as hydroxyl, carbonyl, carbon-carbon double bonds, etc. make it easy to react with Ln 3+ Coordinating to form a stable chelate. Thus, the absorbed energy may be transferred to Ln 3+ Making it sensitive to luminescence.
Compared to small molecules, polymeric materials have many unique advantages, such as tunable structure and topology (linear, hyperbranched, star-shaped or trapezoidal), and multiple functions in different bulk forms. If the AIE fluorescent agent is combined with a high polymer material by a chemical synthesis or physical mixing strategy, the obtained AIE polymer system inherits the advantages of both parties and shows huge potential in application in various fields.
Disclosure of Invention
The invention aims to provide a preparation method of a near-infrared two-region beta-diketone macromolecular rare earth complex with AIE activity.
Preparation of rare earth complex
The invention relates to a preparation method of a near-infrared two-region beta-diketone macromolecular rare earth complex with AIE activity, which comprises the following steps:
(1) synthesis of monohydroxytetraphenylethylene
Adding benzophenone, 4-hydroxybenzophenone and zinc powder into THF, and dropwise adding TiCl under the condition of ice bath in nitrogen atmosphere 4 Then heating to 60-80 ℃, reacting for 20-25 hours, cooling the reactant to room temperature after the reaction is finished, and using K 2 CO 3 Quenching the reaction solution, extracting with ethyl acetate solution and combining the organic phases, MgSO 4 Drying, evaporating the solvent under reduced pressure, and purifying the residue by silica gel column chromatography to obtain 4- (1,2, 2-triphenylvinyl) phenol TPE-OH. Wherein the molar ratio of the benzophenone, the 4-hydroxybenzophenone and the zinc powder is 1:1: 4; the benzophenone and TiCl 4 The molar ratio of (a) to (b) is 1:2 to 1: 3.
(2) Synthesis of double-bond tetraphenylethylene
Addition of allyl Bromide to TPE-OH and K 2 CO 3 Heating and refluxing the DMK solution at 65-70 ℃ for 4-6 hours, cooling to room temperature after the reaction is finished, filtering, evaporating the solvent under reduced pressure, and purifying the residue by silica gel column chromatography to obtain (2- (4- (allyloxy) phenyl) ethylene-1, 1, 2-triphenyl) TPE-OC. Wherein the allyl bromide, TPE-OH and K 2 The molar ratio of CO is 1:1: 1-1: 2: 2.
(3) Synthesis of phenyl beta-diketones
Adding sodium iodide into a DMF (dimethyl formamide) solution of sodium acetylacetonate and 4-chloromethyl styrene, heating to 50-60 ℃, heating for 3-5 hours, cooling to room temperature, diluting the cooled solvent with dichloromethane, filtering, evaporating the solvent under reduced pressure, and purifying the residue by using a silica gel column chromatography to obtain 3- (4-vinylbenzyl) pentane-2, 4-diketone beta-Ph. Wherein the molar ratio of the sodium acetylacetonate to the 4-chloromethyl styrene is 4: 1-5: 1; the molar ratio of the sodium acetylacetonate to the sodium iodide is 8: 1-10: 1.
(4) Synthesis of chain transfer agent CADB
Adding 3-mercaptopropionic acid into an acetone suspension solution containing potassium phosphate, stirring for 1-2 h, adding carbon disulfide, continuously stirring for 1-2 h, adding benzyl bromide, stirring for 0.5-1 h at room temperature, filtering and concentrating filtrate, and adding dichloromethane and potassium chlorideExtracting with saturated aqueous sodium chloride solution, anhydrous MgSO 4 Drying, suction filtering and rotary evaporation of solvent to obtain 2- ((2- (phenylthio) -2-thioethyl) thio) acetic acid CADB. Wherein the molar ratio of the 3-mercaptopropionic acid to the potassium phosphate is 1: 1-1: 2; 1: 3-1: 4 of the 3-mercaptopropionic acid; the molar ratio of the 3-mercaptopropionic acid to the benzyl bromide is 1: 1.
(5) Synthesis of Polymer PTPE
Dissolving TPE-OC, CADB and Azobisisobutyronitrile (AIBN) in a dry DMSO solvent under the nitrogen atmosphere, carrying out polymerization reaction for 20-25 hours at 70-80 ℃, after the reaction is finished, quenching the reaction by using ice water, adding methyl tert-butyl ether for precipitation to obtain white flocculent precipitate, carrying out centrifugal purification, and carrying out vacuum drying to obtain the product poly (2- (4- (allyloxy) phenyl) ethylene-1, 1, 2-triyl) triphenyl PTPE. Wherein the mol ratio of TPE-OC, CADB and azobisisobutyronitrile is 1:1: 0.1.
(6) Synthesis of Block Polymer PTPE-g-beta-DK
Under the nitrogen atmosphere, dissolving PTPE, beta-Ph and azobisisobutyronitrile into a dry DMSO solvent, carrying out polymerization reaction for 20-25 hours at 70-80 ℃, after the reaction is finished, quenching the reaction by using ice water, adding methyl tert-butyl ether for precipitation, carrying out centrifugal purification for three times, and carrying out vacuum drying to obtain the product poly (2- (4- (allyloxy) phenyl) ethylene-1, 1, 2-triyl) triphenyl-b-3- (4-vinylbenzyl) pentane-2, 4-diketone PTPE-g-beta-DK. Wherein the molar ratio of PTPE, beta-Ph and azobisisobutyronitrile is 1:100: 10.
(7) Synthesis of PTPE-g-beta-DK-Nd
Dissolving the PTPE-g-beta-DK in anhydrous Ethyl Acetate (EA) and stirring, adding a neodymium acetate aqueous solution, stirring at room temperature for 2-4 hours, adding an anhydrous ethyl acetate solution of triphenylphosphine oxide, heating to 80 ℃, refluxing and stirring for 10-12 hours, cooling to room temperature after reaction is ended, carrying out vacuum filtration, washing with anhydrous ethyl acetate, and carrying out vacuum drying to obtain the PTPE-g-beta-DK-Nd. Wherein the molar ratio of the PTPE-g-beta-DK to the neodymium acetate is 4: 1-2: 1; the molar ratio of the PTPE-g-beta-DK to the triphenylphosphine oxide is 2: 1-1: 1.
Several principles for designing highly efficient luminescent lanthanide complexes. First, it is difficult to directly excite lanthanide ions due to the forbidden nature of their f-f conversion. However, lanthanide complexes with efficient luminescence can be achieved by coordination of lanthanide ions with strongly absorbing antenna ligands. Secondly, the lanthanide ion needs to accept sufficient energy from the antenna ligand, so the energy gap between the triplet state of the ligand and the acceptance level of the lanthanide ion should be appropriate. Finally, lanthanide ions adopt coordination numbers between 7 and 10; thus, the antenna ligand should have a sufficient number of donors to surround the lanthanide sphere.
The preparation process of the PTPE-g-beta-DK-Nd is shown in figure 1, firstly, a polyterpe macromolecular chain transfer agent PTPE with trithioester at the tail end is synthesized by RAFT active polymerization, and then, a beta-diketone compound with vinyl is initiated and polymerized to finally obtain a block polymer (PTPE-g-beta-DK) containing tetraphenylethylene units and beta-diketone units, wherein the PTPE-g-beta-DK is taken as a first ligand, triphenylphosphine oxide is taken as a second ligand, and Nd is mixed with the first ligand 3+ And (3) carrying out coordination to obtain the polymer lanthanide series AIE fluorescent material (PTPE-g-beta-DK-Nd).
Second, characterization of PTPE-g-beta-DK-Nd
1. GPC data
PTPE, PTPE-g-beta-DK were formulated as 5 mg/mL THF solutions and their molecular weights and relative molecular weight distribution indices were evaluated by GPC. As shown in Table 1, the number average molecular weights (M) of PTPE and PTPE-g-beta-DK n ) And weight average molecular weight (M) w ) 2854, 2874 and 6800, 6854, respectively. Molecular weight distribution index (PDI) values of PTPE, PTPE-g-beta-DK ((PDI))M w /M n ) The values of (A) are 1.007 and 1.008 respectively, and such low PDI represents that the molecular weight distribution of the polymer is concentrated and the molecular weight is uniform, which is very advantageous for the experiment of the later step.
2. Infrared structural characterization
The coordination of the lanthanide compounds was confirmed by comparing the block copolymer PTPE-g- β -DK with the corresponding PTPE-g- β -DK-Nd using IR analysis (FIG. 12). Drawing (A)12 show the IR spectra of PTPE-g-beta-DK and PTPE-g-beta-DK-Nd. At 1560 cm -1 And 1463 cm -1 The two peaks at (a) are the tensile oscillations of C = O and C = C (enol isomer) in the β -diketone group in PTPE-g- β -DK. In the graph of PTPE-g-beta-DK-Nd, the peak was reduced to 1543 cm -1 Represents beta-diketo and Nd 3+ Coordination of (3); 1463 cm due to coordination of enol isomer -1 Retransfer to 1436 cm -1 These data show that Nd 3+ Combined with the beta-diketone group of PTPE-g-beta-DK.
3. XPS data
As can be seen from FIG. 13, compared with the PTPE-g-beta-DK polymer before coordination, the PTPE-g-beta-DK-Nd after coordination not only has Nd-3d and Nd-4d peaks, but also can be seen that the bonding energy of O element before and after coordination is obviously changed, and C element is not changed, which represents Nd 3+ Possibly coordinating with O of PTPE-g-beta-DK. In order to more visually observe the change before and after the bonding, the bonding energy data of each atom in the PTPE-g-beta-DK and the PTPE-g-beta-DK-Nd are shown in Table 2. From the results of XPS analysis, it can be seen that O1s has a change in binding energy of 0.26 eV, and the binding energy is shifted due to Nd 3+ The coordination of C = O of beta-diketone group can affect the shielding effect of inner layer electrons, and the electrons in the complex are transferred to Nd 3+ The shielding effect is weakened and the binding energy of the electrons in the inner layer is moved. The results of XPS spectra were consistent with the IR results, with rare earth ions coordinated to the C = O of the β -diketonate group.
4. Topography characterization
The microstructure and composition of PTPE-g-beta-DK-Nd were observed using TEM and EDS. As shown in fig. 14 (left), the PTPE-g- β -DK-Nd observed in the TEM image is an agglomerated particle, the particle is dense and substantially dispersed, the PTPE-g- β -DK-Nd particle has a spherical or chain-like morphology with distinct boundaries, has a linear structure of a high molecular material with a typical particle size between 80 and 180 nm, which may be related to Nd loading. We also used DLS to study the distribution of PTPE-g- β -DK-Nd in deionized water, the particle size of PTPE-g- β -DK-Nd was mainly between 90-170 nm, and from the inset it can be observed that an aqueous solution of PTPE-g- β -DK-Nd had a pronounced tyndall effect, which demonstrates that PTPE-g- β -DK-Nd particles had formed in the aqueous solution (fig. 14 (right)).
In addition, the composition of the material was further analyzed using TEM/EDS. FIG. 15 shows the EDS spectrum of the element distribution of PTPE-g- β -DK-Nd, as shown by the presence of C, O and Nd in PTPE-g- β -DK-Nd 3+ Three elements, further proving that the PTPE-g-beta-DK-Nd is successfully obtained. EDS-Mapping of FIG. 15 shows C, O, Nd 3+ Distribution analysis of (D), as shown in the figure, C, O, Nd 3+ The PTPE-g-beta-DK-Nd is uniformly distributed in the crystal. Wherein, C and O are the main components of the complex. TEM/EDS results demonstrate Nd 3+ The coordination with the PTPE-g-beta-DK is successfully carried out to form the PTPE-g-beta-DK-Nd.
Third, study of optical Properties
1. Optical property study of TPE-OC
TPE-OC was studied by uv-visible absorption and fluorescence emission spectroscopy (fig. 16). As shown in FIG. 16 (b), the UV-visible spectrum of TPE-OC in THF showed a maximum absorption wavelength at 250 nm and a maximum fluorescence emission wavelength at 475 nm. In addition, the solvent effect of TPE-OH in various solvents was also investigated (FIG. 16 (a). TPE-OC has stronger fluorescence emission in DMSO, MeOH, acetic acid.
2. AIE Effect of TPE-OC
We also examined the AIE properties of TPE-OC containing classical AIE small molecules. Different volume fractions of good solvent (DMSO)/poor solvent (H) were tested 2 O) fluorescence change of TPE-OC in mixed solvent. As shown in FIG. 17 (a), a poor solvent H was added dropwise to a DMSO solution of TPE-OC 2 In the process of O, it can be observed to accompany H 2 The fluorescence intensity of TPE-OC gradually increased to a non-linear degree as the volume fraction of O increased (FIG. 17 (b)), and as H increased 2 After the volume fraction of O is increased to 50%, the phenomenon of TPE-OC is due to the intramolecular free rotation of TPE-OC in a good solvent DMSO solvent,the energy of the excited state is released mainly in the form of non-radiative transition, and when a poor solvent H is added 2 And O, the rotation of the TPE-OC molecules is blocked, and energy can be released only in a mode of radiating the energy earlier. Therefore, the TPE-OC has excellent AIE luminescence property.
3. Optical Properties of PTPE-g-beta-DK-Nd
PTPE-g-. beta. -DK-Nd was observed in the ultraviolet absorption spectrum shown in FIG. 18 (a), and it had three absorption peaks showing Nd 3+ The characteristic absorption of f-f, the strong absorption peak exists mainly because of the existence of PTPE-g-beta-DK ligand, the AIE molecular structure of which inhibits the non-radiative transition, resulting in more energy transfer to Nd 3+ This shows that PTPE-g-beta-DK-Nd is an antenna ligand, and the PTPE-g-beta-DK-Nd has an antenna effect. As shown in FIG. 18 (b), PTPE-g-beta-DK-Nd has two fluorescence emission peaks at 1060nm (Nd) respectively 3+ Is/are as follows 4 F 3/2 - 4 I 11/2 Transition) and 1330 nm: ( 4 F 3/2 - 4 I 13/2 Transition) of Nd, which is 3+ Characteristic emission peak of (1). Therefore, PTPE-g-beta-DK-Nd is a near-infrared two-zone fluorescent probe.
In summary, the invention adopts RAFT active free radical polymerization technology, firstly synthesizes polytetrastyrene PTPE with trithioester at the end, takes the polytetrastyrene PTPE as RAFT macromolecule chain transfer agent to initiate polymerization of beta-diketone monomer containing vinyl, finally obtains block polymer (PTPE-g-beta-DK) containing tetraphenylene unit and beta-diketone unit, takes the block polymer as first ligand, takes triphenylphosphine oxide as second ligand, and Nd 3+ And (3) carrying out coordination to obtain the near-infrared two-region luminescent polymer lanthanide series AIE fluorescent material (PTPE-g-beta-DK-Nd). The structure and the micro-morphology of the PTPE-g-beta-DK-Nd are determined by tests such as IR, XPS, TEM, DLS, TEM-Mapping and the like. TEM and DLS test results show that PTPE-g-beta-DK-Nd is agglomerated particles, has a linear structure of a high polymer material, and the typical particle size is 80-180 nm. The PTPE-g-beta-DK-Nd has fluorescence emission at 1060nm and 1330 nm which belong to the near infrared two-zone range, and can be used as a potential near infrared two-zone bioluminescence probe.
Drawings
FIG. 1 is a scheme of synthesis of PTPE-g- β -DK-Nd;
FIG. 2 is the nuclear magnetic hydrogen spectrum (600 MHz, CDCl 3) of TPE-OH;
FIG. 3 shows the nuclear magnetic carbon spectrum (151 MHz, CDCl) of TPE-OH 3 ）；
FIG. 4 shows the nuclear magnetic hydrogen spectrum (600 MHz, CDCl) of TPE-OC 3 ）；
FIG. 5 shows nuclear magnetic carbon spectrum (151 MHz, CDCl) of TPE-OC 3 ）；
FIG. 6 shows nuclear magnetic hydrogen spectrum (600 MHz, CDCl) of beta-Ph 3 ）；
FIG. 7 shows nuclear magnetic carbon spectrum (151 MHz, CDCl) of beta-Ph 3 ）；
FIG. 8 is nuclear magnetic hydrogen spectrum (600 MHz, DMSO-d 6) of CABD;
FIG. 9 is nuclear magnetic carbon spectrum of CABD (600 MHz, DMSO-d 6);
FIG. 10 is a nuclear magnetic hydrogen spectrum (400 MHz, DMSO-d 6) of PTPE;
FIG. 11 is a nuclear magnetic hydrogen spectrum (600 MHz, DMSO-d 6) of PTPE-g- β -DK;
FIG. 12 is an IR spectrum of PTPE-g- β -DK-Nd;
FIG. 13 is a graph showing the change in XPS binding energy of PTPE-G- β -DK before and PTPE-G-BETA-DK-ND after coordination;
FIG. 14 is a TEM image (left) and a PTPE-g- β -DK-NdDLS image (right) of PTPE-g- β -DK-Nd; (inset: Tyndall effect photograph of aqueous solution of PTPE-g-beta-DK-Nd under laser irradiation);
FIG. 15 is a TEM-EDS elemental scan of PTPE-g- β -DK-Nd (top); a surface scanning picture corresponding to C, O and Nd on PTPE-g-beta-DK-Nd;
FIG. 16 (a) fluorescence spectra of TPE-OC in different solvents; (b) the ultraviolet absorption spectrum and the fluorescence emission spectrum of the TPE-OC;
FIG. 17 (a) fluorescence spectra of TPE-OC at different volume ratios of water to DMSO; (b) the change trend of the corresponding fluorescence intensity of the TPE-OC solution under different volume ratios of water and DMSO;
FIG. 18 shows the UV absorption spectrum (a) and the fluorescence emission spectrum (b) of PTPE-g-. beta. -DK-Nd.
Detailed Description
The preparation method of the near-infrared two-region beta-diketone macromolecular rare earth complex with AIE activity of the invention is further explained in detail by the following specific examples.
The reagents used in the present invention are shown in table 3:
the apparatus used in the present invention is shown in Table 4:
examples
(1) Synthesis of monohydroxytetraphenylethylene (TPE-OH)
Benzophenone (18.22 g, 0.10 mol), 4-hydroxybenzophenone (19.80 g, 0.10 mol), zinc powder (26.16 g, 0.40 mol) and 300.00 mL of THF were charged to a 500 mL three-necked flask and purged three times with nitrogen. Dripping TiCl under the ice bath condition 4 (30.00 mL, 0.27 mol) then warmed to 70 ℃ for 24 hours, after the reaction was complete the reaction was cooled to room temperature and quenched with K 2 CO 3 Quenching the solution, extracting three times with ethyl acetate solution, combining the organic phases, and MgSO 4 Drying and evaporation of the solvent under reduced pressure, the residue was purified by column chromatography on silica gel using ethyl acetate/petroleum ether (v/v 1: 20) as eluent to give 4- (1,2, 2-triphenylvinyl) phenol (TPE-OH) as a yellow solid in yield: 79 percent.
1 H NMR (600 MHz, Chloroform-d) δ(ppm): 7.14-7.02 (m, 12H), 7.01 (td, 3H), 6.93-6.84 (m, 2H), 6.59-6.53 (m, 2H).
13 C NMR (151 MHz, Chloroform-d) δ(ppm): 154.21, 144.00, 143.91, 143.89,
140.48, 140.09, 136.16, 132.68, 131.35, 131.32, 131.30, 128.49, 127.67, 127.57, 126.53, 126.33, 126.21, 114.58, 77.22, 77.00, 76.79.
ESI-MS: m/z calcd for C 26 H 19 O [M+H] - , 347.1414; found 347.1442
(2) Synthesis of double-bond tetraphenylethylene (TPE-OC)
Allyl bromide (12.10 g, 0.10 mol) was added dropwise over 15 minutes to 40 mL of TPE-OH (34.82 g, 0.10 mol) and K 2 CO 3 (13.82 g, 0.10 mol) in DMK followed by heating at 65 ℃ under reflux for 5 h, cooling to room temperature after the reaction is complete, filtration and evaporation of the solvent under reduced pressure, purification of the residue by column chromatography on silica gel using ethyl acetate/petroleum ether (v/v 1: 20) as eluent to give (2- (4- (allyloxy) phenyl) ethylene-1, 1, 2-triyl) triphenyl (TPE-OC) as a white solid in yield: 44 percent.
1 H NMR (600 MHz, Chloroform-d) δ(ppm): 7.13-6.98 (m, 15H), 6.94-6.89 (m, 2H), 6.66-6.59 (m, 2H), 6.06-5.96 (m, 1H), 5.37 (dq, 1H), 5.25 (dt, 1H), 4.44 (dt, 2H).
13 C NMR (151 MHz, Chloroform-d) δ(ppm): 158.25, 158.17, 143.76, 143.28, 140.76, 137.88, 136.00, 135.91, 133.01, 132.52, 132.49, 131.31, 130.82, 127.78, 126.27, 119.98, 113.18, 113.00, 55.09, 55.06, 29.30, 27.19.
ESI-MS: m/z calcd for C 29 H 25 O [M+H] + , 389.1827; found 389.1819.
(3) Synthesis of phenyl beta-diketone (beta-Ph)
To a solution of sodium acetylacetonate (4.59 g, 32.70 mmol) and 4-chloromethylstyrene (1.00 g, 6.55 mmol) in 40 mL of DMF was added sodium iodide (NaI) (3.28 mmol, 0.49 g), the temperature was raised to 60 ℃, after heating for 4 hours, the mixture was cooled to room temperature, the cooled solvent was diluted with 30 mL of dichloromethane and filtered, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography using chloroform/dichloromethane (v/v 1: 15) as an eluent to give 3- (4-vinylbenzyl) pentane-2, 4-dione (β -Ph) as a yellow oil, yield: 38 percent.
1 H NMR (600 MHz, Chloroform-d) δ(ppm): 7.35-7.29 (m, 2H), 7.18-7.12 (m, 2H), 6.68 (d, 1H), 5.70 (d, 1H), 5.20 (d, 1H), 2.88 (t, 2H), 2.13 (s, 3H), 1.30-1.23 (m, 3H).
13 C NMR (151 MHz, Chloroform-d) δ(ppm): 206.64, 136.28, 136.21, 135.63, 130.89, 129.89, 128.82, 128.78, 127.57, 126.54, 113.77, 72.09, 30.17, 29.71.
ESI-MS: m/z calcd for C 14 H 17 O 2 [M+H] + , 217.1150; found 217.1223.
(4) Synthesis of chain transfer agent (CADB)
3-mercaptopropionic acid (1.00 g, 9.43 mmol) was added to a solution containing potassium phosphate (K) 3 PO 4 ) (2.00 g, 9.43 mmol) was stirred for 1 hour in 20.00 mL of acetone suspension. Carbon disulfide (1.71 mL, 28.30 mmol) was added and stirred for 1 hour. Benzyl bromide (1.12 mL, 9.43 mmol) was added and stirred at room temperature for 30 min. The filtrate was concentrated by filtration and extracted three times with methylene chloride and saturated aqueous sodium chloride (NaCl) solution, anhydrous MgSO 4 Dry overnight. Suction filtration and rotary evaporation of the solvent gave 2- ((2- (phenylthio) -2-thioethyl) thio) acetic acid (CADB) as a yellow solid in yield: 71 percent.
1 H NMR (600 MHz, DMSO-d 6 ) δ(ppm): 7.40-7.34 (m, 2H), 7.33-7.28 (m, 2H), 7.28-7.23 (m, 1H), 3.52 (t, 2H), 2.65 (t, 2H), 2.48 (dt, 1H).
13 C NMR (151 MHz, DMSO-d 6 ) δ(ppm): 223.82, 172.89, 135.55, 129.36 (2C), 40.60 (2C), 39.97 (2C, 32.50 (2C).
ESI-MS: m/z calcd for C 10 H 10 O 2 S 3 [M] + , 257.9843; found 257.9805.
(5) Synthesis of Polymer (PTPE)
TPE-OC (0.50 mmol, 194.20 mg), CADB (0.50 mmol, 128.99 mg), Azobisisobutyronitrile (AIBN) (0.05 mmol, 8.20 mg) were dissolved in 30.00 mL of dry DMSO solvent under nitrogen atmosphere and polymerized at 75 ℃ for 24 hours. After the reaction is finished, quenching the reaction by ice water, adding 100.0 mL of methyl tert-butyl ether for precipitation to obtain white flocculent precipitate, centrifugally purifying for three times, and drying in vacuum to obtain the product poly (2- (4- (allyloxy) phenyl) ethylene-1, 1, 2-triyl) triphenyl (PTPE), wherein the yield is as follows: and 43 percent.
1 H NMR (400 MHz, DMSO-d 6 ) δ(ppm): 7.10 (q, aromatic backbone), 6.94 (t,
aromatic backbone), 6.86–6.81 (m, aromatic backbone), 6.72–6.67 (m, aromatic backbone), 4.45 (d, O-CH 2 -CH), 1.98 (q, S-CH 2 =S).
(6) Synthesis of Block Polymer (PTPE-g-. beta. -DK)
PTPE (0.05 mmol), β -Ph (1.08 g, 5.00 mmol), and AIBN (0.08 g, 0.50 mmol) were dissolved in 30.0 mL of dry DMSO solvent under a nitrogen atmosphere, and polymerization was carried out at 75 ℃ for 24 hours. After the reaction is finished, quenching the reaction by ice water, adding 100.00 mL of methyl tert-butyl ether for precipitation, centrifuging and purifying for three times, and drying in vacuum to obtain the product poly (2- (4- (allyloxy) phenyl) ethylene-1, 1, 2-triyl) triphenyl-b-3- (4-vinyl benzyl) pentane-2, 4-diketone (PTPE-g-beta-DK), wherein the yield is as follows: and 55 percent.
1 H NMR (600 MHz, DMSO-d 6 ) δ(ppm): 7.93 (s, aromatic backbone), 7.34 – 6.84 (m, aromatic backbone), 6.63 (s, aromatic backbone), 4.07 (q, O-CH 2 -CH), 3.14 (d, -CH 2 -CH-), 2.87 (s, S-CH 2 =S), 2.71 (d, CH 3 -C=O).
(7) Synthesis of PTPE-g-beta-DK-Nd
Poly (2- (4- (allyloxy) phenyl) ethylene-1, 1, 2-triyl) triphenyl-b-3- (4-vinylbenzyl) pentane-2, 4-dione (3.00 mmol) is dissolved in 10 mL of anhydrous EA and placed in a 50.00 mL round bottom flask with magnetic stirring. Neodymium acetate (0.34 g, 1.00 mmol) was dissolved in 1 mL of water and slowly added to the above solution. After stirring at room temperature for 3 hours, a solution of triphenylphosphine oxide (0.56 g, 2.00 mmol) dissolved in 5.00 mL of anhydrous EA was added dropwise, the temperature was raised to 80 ℃ and the mixture was stirred under reflux for 12 hours, after the reaction was terminated, the temperature was lowered to room temperature. Vacuum filtration, washing with anhydrous EA for 3 times, and vacuum drying at 70 deg.C for 8 hr to obtain purple solid PTPE-g-beta-DK-Nd with yield: 53 percent.
Claims (8)
1. A preparation method of near-infrared two-region beta-diketone macromolecular rare earth complex with AIE activity comprises the following steps:
(1) synthesis of monohydroxytetraphenylethylene: adding benzophenone, 4-hydroxybenzophenone and zinc powder into THF, and dropwise adding TiCl under the condition of ice bath in nitrogen atmosphere 4 Then heating to 60-80 ℃, reacting for 20-25 hours, cooling the reactant to room temperature after the reaction is finished, and adding K 2 CO 3 Quenching the reaction solution, extracting with ethyl acetate solution and combining the organic phases, MgSO 4 Drying, evaporating the solvent under reduced pressure, and purifying the residue by silica gel column chromatography to obtain 4- (1,2, 2-triphenylvinyl) phenol TPE-OH;
(2) synthesis of double-bond tetraphenylethylene: addition of allyl Bromide to TPE-OH and K 2 CO 3 Heating and refluxing the DMK solution for 4-6 hours at 65-70 ℃, cooling to room temperature after the reaction is finished, filtering, evaporating the solvent under reduced pressure, and purifying the residue by silica gel column chromatography to obtain (2- (4- (allyloxy) phenyl) ethylene-1, 1, 2-triphenyl) TPE-OC;
(3) synthesis of phenyl beta-diketones: adding sodium iodide into a DMF (dimethyl formamide) solution of sodium acetylacetonate and 4-chloromethyl styrene, heating to 50-60 ℃, heating for 3-5 hours, cooling to room temperature, diluting the cooled solvent with dichloromethane, filtering, evaporating the solvent under reduced pressure, and purifying the residue by using a silica gel column chromatography to obtain 3- (4-vinylbenzyl) pentane-2, 4-diketone beta-Ph;
(4) synthesis of chain transfer agent CADB: adding 3-mercaptopropionic acid into an acetone suspension solution containing potassium phosphate, stirring for 1-2 h, adding carbon disulfide, continuously stirring for 1-2 h, adding benzyl bromide, stirring for 0.5-1 h at room temperature, filtering, concentrating filtrate, extracting with dichloromethane and saturated sodium chloride aqueous solution, and removing anhydrous MgSO (MgSO) by using a solvent 4 Drying, carrying out suction filtration, and carrying out rotary evaporation on the solvent to obtain 2- ((2- (phenylthio) -2-thioethyl) thio) acetic acid CADB;
(5) synthesis of Polymer PTPE: dissolving TPE-OC, CADB and azobisisobutyronitrile in a dry DMSO solvent in a nitrogen atmosphere, carrying out polymerization reaction for 20-25 hours at 70-80 ℃, quenching the reaction with ice water after the reaction is finished, adding methyl tert-butyl ether for precipitation to obtain white flocculent precipitate, carrying out centrifugal purification, and carrying out vacuum drying to obtain a product poly (2- (4- (allyloxy) phenyl) ethylene-1, 1, 2-triyl) triphenyl PTPE;
(6) synthesis of Block Polymer PTPE-g-beta-DK: dissolving PTPE, beta-Ph and azobisisobutyronitrile into a dry DMSO solvent in a nitrogen atmosphere, carrying out polymerization reaction for 20-25 hours at 70-80 ℃, quenching the reaction with ice water after the reaction is finished, adding methyl tert-butyl ether for precipitation, carrying out centrifugal purification for three times, and carrying out vacuum drying to obtain a product poly (2- (4- (allyloxy) phenyl) ethylene-1, 1, 2-triyl) triphenyl-b-3- (4-vinylbenzyl) pentane-2, 4-diketone PTPE-g-beta-DK;
(7) synthesis of PTPE-g-beta-DK-Nd: dissolving the PTPE-g-beta-DK in anhydrous ethyl acetate, stirring, adding a neodymium acetate aqueous solution, stirring at room temperature for 2-4 hours, adding an anhydrous ethyl acetate solution of triphenylphosphine oxide, heating to 80 ℃, refluxing and stirring for 10-12 hours, cooling to room temperature after reaction is finished, carrying out vacuum filtration, washing with anhydrous ethyl acetate, and carrying out vacuum drying to obtain the PTPE-g-beta-DK-Nd.
2. The method for preparing near-infrared two-region beta-diketone macromolecular rare earth complex with AIE activity according to claim 1, which is characterized in that: in the step (1), the molar ratio of the benzophenone, the 4-hydroxybenzophenone and the zinc powder is 1:1: 4; the benzophenone and TiCl 4 The molar ratio of (a) to (b) is 1:2 to 1: 3.
3. The method for preparing near-infrared two-region beta-diketone macromolecular rare earth complex with AIE activity according to claim 1, characterized in that: in the step (2), the allyl bromide, TPE-OH and K 2 The molar ratio of CO is 1:1: 1-1: 2: 2.
4. The method for preparing near-infrared two-region beta-diketone macromolecular rare earth complex with AIE activity according to claim 1, which is characterized in that: in the step (3), the molar ratio of the sodium acetylacetonate to the 4-chloromethyl styrene is 4: 1-5: 1; the molar ratio of the sodium acetylacetonate to the sodium iodide is 8: 1-10: 1.
5. The method for preparing near-infrared two-region beta-diketone macromolecular rare earth complex with AIE activity according to claim 1, which is characterized in that: in the step (4), the molar ratio of the 3-mercaptopropionic acid to the potassium phosphate is 1: 1-1: 2; 1: 3-1: 4 of the 3-mercaptopropionic acid; the molar ratio of the 3-mercaptopropionic acid to the benzyl bromide is 1: 1.
6. The method for preparing near-infrared two-region beta-diketone macromolecular rare earth complex with AIE activity according to claim 1, which is characterized in that: in the step (5), the molar ratio of TPE-OC, CADB and azobisisobutyronitrile is 1:1: 0.1.
7. The method for preparing near-infrared two-region beta-diketone macromolecular rare earth complex with AIE activity according to claim 1, which is characterized in that: in the step (6), the molar ratio of PTPE, beta-Ph and azobisisobutyronitrile is 1:100: 10.
8. The method for preparing near-infrared two-region beta-diketone macromolecular rare earth complex with AIE activity according to claim 1, which is characterized in that: in the step (7), the molar ratio of the PTPE-g-beta-DK to the neodymium acetate is 4: 1-2: 1; the molar ratio of the PTPE-g-beta-DK to the triphenylphosphine oxide is 2: 1-1: 1.
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