CN114853962B - 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
- Publication number
- CN114853962B CN114853962B CN202210575476.2A CN202210575476A CN114853962B CN 114853962 B CN114853962 B CN 114853962B CN 202210575476 A CN202210575476 A CN 202210575476A CN 114853962 B CN114853962 B CN 114853962B
- Authority
- CN
- China
- Prior art keywords
- beta
- ptpe
- diketone
- near infrared
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of near infrared two-zone beta-diketone macromolecule rare earth complex with AIE activity, which adopts RAFT active free radical polymerization technology to synthesize polytetrastyrene PTPE with trithio ester at the end, takes the 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 tetraphenyl unit and beta-diketone unit, takes the PTPE as a first ligand, takes triphenylphosphine oxide as a second ligand, and reacts with Nd 3+ Coordination is carried out to obtain the near infrared two-region luminous polymer lanthanide AIE fluorescent material (PTPE-g-beta-DK-Nd). TEM and DLS test results show that PTPE-g-beta-DK-Nd is agglomerated particles, and has a linear structure of a high polymer material, and the typical particle size is 80-180 nm. PTPE-g-beta-DK-Nd has fluorescence emission at 1060nm and 1330 nm which belong to the range of the near infrared two regions, and can be used as a potential near infrared two-region bioluminescence probe.
Description
Technical Field
The invention relates to a preparation method of a near infrared two-zone beta-diketone macromolecular rare earth complex with AIE activity, belonging to the technical field of fluorescent material preparation.
Background
In recent years, the ratiometric fluorescence method based on antenna effect has attracted great attention. Ln (Ln) 3+ Has a small molar absorption coefficient and a weak light absorption capacity. In addition, the 4f-4f transition is hindered, all of which result in low luminous efficiency. Some have strong absorptionThe sexual chromophore compound will transfer the absorbed energy to Ln 3+ This causes an antenna effect, thereby making Ln 3+ Luminescence sensitization. Beta-diketones, porphyrin derivatives are common antenna ligands. In addition, the functional groups such as hydroxyl, carbonyl, carbon-carbon double bond and the like facilitate the reaction with Ln 3+ Coordination forms a stable chelate. Thus, the absorbed energy can be transferred to Ln 3+ Making it luminescence sensitive.
Compared to small molecules, polymeric materials have many unique advantages such as adjustable structure and topology (linear, hyperbranched, star-shaped or trapezoid-shaped), and multiple functions in different blocks. If the AIE fluorescent agent is combined with the high molecular material through a chemical synthesis or physical mixing strategy, the obtained AIE polymer system has the advantages of both sides, and has great potential in application in various fields.
Disclosure of Invention
The invention aims to provide a preparation method of a near infrared two-zone beta-diketone macromolecular rare earth complex with AIE activity.
1. Preparation of rare earth complexes
The invention relates to a preparation method of a near infrared two-zone beta-diketone macromolecular rare earth complex with AIE activity, which comprises the following steps:
(1) Synthesis of monohydroxy tetraphenyl ethylene
Adding diphenyl ketone, 4-hydroxy diphenyl ketone and zinc powder into THF, and dropping 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 The reaction was quenched with ethyl acetate solution, extracted and the organic phases combined, dried over MgSO 4 Drying, evaporating the solvent under reduced pressure, and purifying the residue by silica gel column chromatography to obtain 4- (1, 2-triphenylvinyl) phenol TPE-OH. Wherein, the molar ratio of the diphenyl ketone, the 4-hydroxy diphenyl ketone and the zinc powder is 1:1:4; the diphenyl ketone and TiCl 4 The molar ratio of (2) is 1:2-1:3.
(2) Synthesis of double bond tetraphenyl ethylene
Allyl bromideAdded to TPE-OH and K 2 CO 3 In the DMK solution of (2) - (4- (allyloxy) phenyl) ethylene-1, 2-tri-phenyl TPE-OC is obtained by heating and refluxing for 4-6 hours at 65-70 ℃, cooling to room temperature after the reaction is finished, filtering, decompressing and evaporating the solvent, and purifying the residue by using a silica gel column chromatography. Wherein the allyl bromide, TPE-OH and K 2 The molar ratio of CO is 1:1:1 to 1:2:2.
(3) Synthesis of phenyl beta-diketones
Sodium iodide is added into DMF solution of sodium acetylacetonate and 4-chloromethyl styrene, the temperature is raised to 50-60 ℃, after heating for 3-5 hours, the mixture is cooled to room temperature, the cooled solvent is diluted by methylene dichloride and then filtered, the solvent is evaporated under reduced pressure, and the residue is purified by silica gel column chromatography, so that 3- (4-vinylbenzyl) pentane-2, 4-diketone beta-Ph is obtained. 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, concentrating the filtrate, extracting with dichloromethane and saturated sodium chloride aqueous solution, and anhydrous MgSO 4 Drying, suction filtration and rotary evaporation of the solvent gave 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; the ratio of the 3-mercaptopropionic acid to the water is 1:3-1:4; the molar ratio of the 3-mercaptopropionic acid to the benzyl bromide is 1:1.
(5) Synthesis of the Polymer PTPE
Under the nitrogen atmosphere, TPE-OC, CADB and Azodiisobutyronitrile (AIBN) are dissolved in a dry DMSO solvent and are polymerized for 20-25 hours at 70-80 ℃, after the reaction is finished, ice water is used for quenching the reaction, methyl tertiary butyl ether is added for precipitation, white flocculent precipitate is obtained, centrifugal purification is carried out, and the product poly (2- (4- (allyloxy) phenyl) ethylene-1, 2-tri-yl) triphenylPTPE is obtained after vacuum drying. Wherein, the mol ratio of TPE-OC, CADB and azodiisobutyronitrile is 1:1:0.1.
(6) Synthesis of block Polymer PTPE-g-beta-DK
Under the nitrogen atmosphere, dissolving PTPE, beta-Ph and azodiisobutyronitrile in a dry DMSO solvent, carrying out polymerization reaction for 20-25 hours at 70-80 ℃, quenching the reaction with ice water after the reaction is finished, adding methyl tertiary butyl ether for precipitation, centrifugally purifying for three times, and carrying out vacuum drying to obtain the product poly (2- (4- (allyloxy) phenyl) ethylene-1, 2-tri) triphenyl-b-3- (4-vinylbenzyl) pentane-2, 4-diketone PTPE-g-beta-DK. Wherein the mole ratio of PTPE, beta-Ph and azodiisobutyronitrile is 1:100:10.
(7) Synthesis of PTPE-g-beta-DK-Nd
Dissolving PTPE-g-beta-DK in anhydrous Ethyl Acetate (EA), stirring, adding an aqueous solution of neodymium acetate, stirring for 2-4 hours at room temperature, adding an anhydrous ethyl acetate solution of triphenylphosphine oxide, heating to 80 ℃, refluxing and stirring for 10-12 hours, cooling to room temperature after the reaction is ended, vacuum-filtering, washing with the anhydrous ethyl acetate, and vacuum-drying to obtain PTPE-g-beta-DK-Nd. Wherein the mole ratio of PTPE-g-beta-DK to neodymium acetate is 4:1-2:1; the molar ratio of PTPE-g-beta-DK to triphenylphosphine oxide is 2:1-1:1.
Several principles of designing highly efficient luminescent lanthanide complexes. First, it is difficult to directly excite lanthanide ions due to the forbidden nature of the f-f conversion of lanthanide ions. However, lanthanide complexes with efficient luminescence can be achieved by coordination of lanthanide ions with strongly absorptive antenna ligands. Second, the lanthanide ion needs to receive enough energy from the antenna ligand, so the energy gap between the tristate of the ligand and the received energy level of the lanthanide ion should be appropriate. Finally, lanthanide ions employ 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 PTPE-g-beta-DK-Nd is shown in figure 1, a polymer TPE macromolecular chain transfer agent PTPE with trithio ester at the tail end is firstly synthesized by RAFT active polymerization, and then a beta-diketone compound with vinyl is initiated to polymerize, so that a block polymer (PTPE-g-beta-DK) containing a tetraphenyl ethylene unit and a beta-diketone unit is finally obtained, and the block polymer is taken as a first ligand, and triphenylphosphine oxide is taken as a second ligandBody, and Nd 3+ And (3) coordination is carried out to obtain the polymer lanthanide AIE fluorescent material (PTPE-g-beta-DK-Nd).
2. Characterization of PTPE-g-beta-DK-Nd
1. GPC data
PTPE, PTPE-g- β -DK were formulated as 5 mg/mL THF solutions, and their molecular weights and relative molecular weight distribution indexes were evaluated by GPC. As shown in Table 1, the number average molecular weights (M 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-DKM w /M n ) Such low PDI represents a more concentrated distribution of molecular weights and a more uniform molecular weight of the polymer, which is highly advantageous for the later experiments, respectively, with values of 1.007 and 1.008.
2. Infrared structural characterization
Coordination of the lanthanide compounds was confirmed by comparing the block copolymers PTPE-g- β -DK with the corresponding PTPE-g- β -DK-Nd using IR analysis (FIG. 12). FIG. 12 shows 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 are the stretching vibrations of c=o and c=c (enol isomer) in the β -diketone group in the PTPE-g- β -DK. In the graph of PTPE-g-beta-DK-Nd, the peak was reduced to 1543 cm -1 Represents beta-diketone group and Nd 3+ Coordination of (d); 1463 cm due to enol isomer and coordination -1 Move again to 1436 cm -1 These data indicate that Nd 3+ Bind to the β -diketone group of PTPE-g- β -DK.
3. XPS data
As can be seen from FIG. 13, the PTPE-g- β -DK-Nd after coordination showed not only Nd-3d, nd-4d peaks, but also a significant change in the binding energy of O element before and after coordination, while the C element did not change, which represents Nd 3+ Possibly with PTPCoordination of the O of E-g-beta-DK occurs. In order to more intuitively observe the change before and after the binding, the binding energy data of each atom in PTPE-g-beta-DK and PTPE-g-beta-DK-Nd are shown in Table 2. From analysis of XPS results, it was found that the binding energy of O1s was changed by 0.26 and eV, and the movement of the binding energy was due to Nd 3+ C=o coordination with β -diketone group affects the shielding effect of internal electrons, and electrons in the complex transfer to Nd 3+ On the outer empty track of the (c), the shielding effect will be weakened and the binding energy of the inner electrons will be moved. The result of XPS spectrum is consistent with IR result, and rare earth ion coordinates with c=o of β -diketone group.
。
4. Characterization of topography
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, dense and substantially dispersed, with a spherical or chain-like morphology with distinct boundaries of PTPE-g- β -DK-Nd particles, with a linear structure of polymeric material, with typical particle sizes between 80-180 nm, which may be related to Nd loading. We have 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 and nm, and from the inset, it was observed that the aqueous solution of PTPE-g- β -DK-Nd had a significant tyndall effect, which demonstrated 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 an EDS spectrum of the elemental distribution of PTPE-g- β -DK-Nd, as shown by the presence of C, O and Nd in PTPE-g- β -DK-Nd 3+ The success of obtaining PTPE-g-beta-DK-Nd was further confirmed by three elements. EDS-Mapping of FIG. 15 shows C, O, nd 3+ Distribution analysis of (5), as shown in FIG. C, O, nd 3+ Is uniformly distributed in PTPE-g-beta-DK-Nd. Wherein C and O are main components of the complex. TEM/EDS results demonstrate Nd 3+ Has been successful with PTThe PE-g-beta-DK coordinates to form PTPE-g-beta-DK-Nd.
3. 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-vis spectrum of TPE-OC in THF exhibits 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 studied (FIG. 16 (a.) TPE-OC has a strong 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 the mixed solvent. As shown in FIG. 17 (a), poor solvent H was added dropwise to a DMSO solution of TPE-OC 2 In the course of O, it is observed that with H 2 Increasing volume fraction of O, the fluorescence intensity of TPE-OC increases gradually in a non-linear fashion (FIG. 17 (b)), and when H 2 After the volume fraction of O is increased to 50%, the phenomenon of TPE-OC is caused by free rotation in the molecular of TPE-OC in the good solvent DMSO, and the energy of the excited state is mainly released in a non-radiative transition mode, and when the poor solvent H is added 2 At O, the TPE-OC molecule rotation is hindered, where energy is released only in a radiation-front fashion. Thus, TPE-OC has excellent AIE luminescence properties.
3. Optical Properties of PTPE-g-beta-DK-Nd
PTPE-g-beta-DK-Nd was found in the ultraviolet absorption spectrum shown in FIG. 18 (a), which had three absorption peaks, showing Nd 3+ The f-f characteristic absorption of (2) and the presence of strong absorption peaks is mainly due to the presence of PTPE-g-beta-DK ligand, the AIE molecular structure of which inhibits non-radiative transitions, resulting in more energy transfer to Nd 3+ This indicates that PTPE-g-beta-DK-Nd is an antenna ligand, and that PTPE-g-beta-DK-Nd has an antenna effect. As shown in FIG. 18 (b), the PTPE-g-beta-DK-Nd has two fluorescence emission peaks, which are dividedAre located separately at 1060nm (Nd) 3+ A kind of electronic device 4 F 3/2 - 4 I 11/2 Transition) and 1330 nm 4 F 3/2 - 4 I 13/2 Transition), this is Nd 3+ Is characterized by an emission peak. Thus, PTPE-g-beta-DK-Nd is a near infrared two-region fluorescent probe.
In summary, the invention adopts RAFT living radical polymerization technology to synthesize the PTPE with trithio ester at the tail end, takes the PTPE as RAFT polymer chain transfer agent to initiate polymerization of beta-diketone monomer containing vinyl, finally obtains the block polymer (PTPE-g-beta-DK) containing tetraphenyl ethylene unit and beta-diketone unit, takes the PTPE as a first ligand, takes triphenylphosphine oxide as a second ligand and reacts with Nd 3+ Coordination is carried out to obtain the near infrared two-region luminous polymer lanthanide AIE fluorescent material (PTPE-g-beta-DK-Nd). The structure and the microstructure of PTPE-g-beta-DK-Nd are determined through a test 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, and has a linear structure of a high polymer material, and the typical particle size is 80-180 nm. PTPE-g-beta-DK-Nd has fluorescence emission at 1060nm and 1330 nm which belong to the range of the near infrared two regions, and can be used as a potential near infrared two-region bioluminescence probe.
Drawings
FIG. 1 is a synthetic route diagram of PTPE-g-beta-DK-Nd;
FIG. 2 is a 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 the nuclear magnetic carbon spectrum (151 MHz, CDCl) of TPE-OC 3 ）；
FIG. 6 shows a nuclear magnetic hydrogen spectrum of β -Ph (600 MHz, CDCl 3 ）；
FIG. 7 shows a nuclear magnetic carbon spectrum of β -Ph (151 MHz, CDCl 3 ）；
FIG. 8 is a nuclear magnetic hydrogen spectrum (600 MHz, DMSO-d 6) of CABD;
FIG. 9 is a nuclear magnetic carbon spectrum (600 MHz, DMSO-d 6) of CABD;
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 infrared spectrum of PTPE-g- β -DK-Nd;
FIG. 13 is a graph showing XPS binding energy change between PTPE-G-beta-DK before coordination and PTPE-G-beta-DK-ND after coordination;
FIG. 14 is a TEM image of PTPE-g- β -DK-Nd (left) and a PTPE-g- β -DK-NdDLS image (right); (inset: a photograph of the tyndall effect of an aqueous solution of PTPE-g-beta-DK-Nd under laser irradiation);
FIG. 15 is a TEM-EDS elemental scan spectrum of PTPE-g- β -DK-Nd (top); c, O on PTPE-g-beta-DK-Nd and corresponding surface scanning pictures of three elements Nd;
FIG. 16 (a) fluorescence spectra of TPE-OC in different solvents; (b) ultraviolet absorption spectrum and fluorescence emission spectrum of TPE-OC;
FIG. 17 (a) fluorescence spectra of TPE-OC at different water and DMSO volume ratios; (b) Corresponding trend of fluorescence intensity of the TPE-OC solution under different water and DMSO volume ratios;
fig. 18 shows ultraviolet absorption spectrum (a) and fluorescence emission spectrum (b) of PTPE-g- β -DK-Nd.
Detailed Description
The preparation method of the near infrared two-zone beta-diketone macromolecular rare earth complex with AIE activity is further described in detail by specific examples.
The reagents used in the present invention are as shown in Table 3:
the apparatus used in the present invention is shown in Table 4:
examples
(1) Synthesis of monohydroxy tetraphenyl ethylene (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 THF were charged into a 500 mL three-necked flask, and purged three times with nitrogen. TiCl is added dropwise under ice bath condition 4 (30.00 mL,0.27 mol) then heating to 70℃for 24 hours, cooling the reaction mixture to room temperature, and then using K 2 CO 3 The solution was quenched and the combined organic phases were extracted three times with ethyl acetate solution and dried over MgSO 4 Drying, evaporation of the solvent under reduced pressure, purification of the residue by silica gel column chromatography using ethyl acetate/petroleum ether (v/v 1:20) as eluent gave 4- (1, 2-triphenylvinyl) phenol (TPE-OH) as a yellow solid in yield: 79 Percent of the total weight of the composition.
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 tetraphenyl ethylene (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 refluxing at 65℃for 5 hours, cooling to room temperature after completion of the reaction, filtering, evaporating the solvent under reduced pressure, purifying the residue by silica gel column chromatography using ethyl acetate/petroleum ether (v/v 1:20) as eluent to give(2- (4- (allyloxy) phenyl) ethylene-1, 2-tri-yl) triphenyl (TPE-OC) to a white solid, yield: 44 Percent of the total weight of the composition.
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-diketones (beta-Ph)
Sodium iodide (NaI) (3.28 mmol,0.49 g) was added to a solution of sodium acetylacetonate (4.59 g,32.70 mmol) and 4-chloromethylstyrene (1.00 g,6.55 mmol) in 40 mL DMF, warmed to 60℃and cooled to room temperature after 4 hours, 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 eluent to give 3- (4-vinylbenzyl) pentane-2, 4-dione (. Beta. -Ph) as a yellow oil, yield: 38 Percent of the total weight of the composition.
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) of the mixture was added with potassium phosphate (K) 3 PO 4 ) (2.00 g,9.43 mmol) in a suspension of 20.00 g/mL mmol in acetone was stirred for 1 hour. Carbon disulphide (1.71 mL,28.30 mmol) is added and stirred for 1 hour. Benzyl bromide (1.12 mL,9.43 mmol) was added and stirred at room temperature for 30 minutes. Filtering and concentrating the filtrate, extracting with dichloromethane and saturated sodium chloride (NaCl) water solution three times, and anhydrous MgSO 4 Drying overnight. Suction filtration and rotary evaporation of the solvent gave 2- ((2- (phenylthio) -2-thioethyl) thio) acetic acid (CADB) as a yellow solid, yield: 71 Percent of the total weight of the composition.
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 dry DMSO solvent under nitrogen and polymerized at 75deg.C for 24 hours. After the reaction is finished, quenching the reaction by ice water, adding 100.0 mL methyl tertiary butyl ether for precipitation to obtain white flocculent precipitate, centrifuging and purifying for three times, and vacuum drying to obtain the product poly (2- (4- (allyloxy) phenyl) ethylene-1, 2-tri) triphenyl (PTPE), wherein the yield is: 43 Percent of the total weight of the composition.
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), beta-Ph (1.08 g,5.00 mmol), AIBN (0.08 g,0.50 mmol) were dissolved in dry DMSO solvent of 30.0. 30.0 mL under nitrogen atmosphere and polymerized at 75℃for 24 hours. After the reaction is finished, quenching the reaction with ice water, adding 100.00 mL methyl tertiary butyl ether for precipitation, centrifuging and purifying for three times, and vacuum drying to obtain a product poly (2- (4- (allyloxy) phenyl) ethylene-1, 2-tri) triphenyl-b-3- (4-vinylbenzyl) pentane-2, 4-dione (PTPE-g-beta-DK), wherein the yield is: 55 Percent of the total weight of the composition.
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, 2-tri-yl) triphenyl-b-3- (4-vinylbenzyl) pentane-2, 4-dione (3.00 mmol) was dissolved in 10 mL anhydrous EA, placed in a 50.00 mL round bottom flask and magnetically stirred. Neodymium acetate (0.34 g,1.00 mmol) was dissolved in 1 mL water and added slowly to the solution. After stirring at room temperature for 3 hours, a solution of triphenylphosphine oxide (0.56 g,2.00 mmol) in 5.00 mL anhydrous EA was added dropwise, the temperature was raised to 80℃and stirred at reflux for 12 hours, and after the reaction was terminated, the temperature was lowered to room temperature. Vacuum filtration and washing with anhydrous EA for 3 times, and vacuum drying at 70℃for 8 hours, gave PTPE-g- β -DK-Nd as a purple solid in yield: 53 Percent of the total weight of the composition.
Claims (6)
1. The preparation method of the near infrared two-zone beta-diketone macromolecular rare earth complex with AIE activity comprises the following steps:
(1) Synthesis of monohydroxy tetraphenyl ethylene: adding diphenyl ketone, 4-hydroxy diphenyl ketone and zinc powder into THF, and dropping 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 with ethyl acetate solutionThe organic phases were extracted and combined, using MgSO 4 Drying, evaporating the solvent under reduced pressure, and purifying the residue by silica gel column chromatography to obtain 4- (1, 2-triphenylvinyl) phenol TPE-OH;
(2) Synthesis of double-bond tetraphenyl ethylene: allyl bromide was added to TPE-OH and K 2 CO 3 Heating and refluxing for 4-6 hours at 65-70 ℃, cooling to room temperature after the reaction is finished, filtering, decompressing and evaporating the solvent, and purifying the residue by using a silica gel column chromatography to obtain (2- (4- (allyloxy) phenyl) ethylene-1, 2-tri) triphenyl TPE-OC;
(3) Synthesis of phenyl beta-diketones: adding sodium iodide into DMF 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 silica gel column chromatography to obtain 3- (4-vinylbenzyl) pentane-2, 4-dione 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 the filtrate, extracting with dichloromethane and saturated sodium chloride aqueous solution, and anhydrous MgSO 4 Drying, suction filtration and rotary evaporation of the solvent to give 2- ((2- (phenylthio) -2-thioethyl) thio) acetic acid CADB;
(5) Synthesis of polymer PTPE: under the nitrogen atmosphere, dissolving TPE-OC, CADB and azodiisobutyronitrile in a dry DMSO solvent, carrying out polymerization reaction for 20-25 hours at 70-80 ℃, quenching the reaction with ice water after the reaction is finished, adding methyl tertiary butyl ether for precipitation to obtain white flocculent precipitate, centrifuging and purifying, and carrying out vacuum drying to obtain a product poly (2- (4- (allyloxy) phenyl) ethylene-1, 2-tri) triphenyl PTPE;
(6) Synthesis of Block Polymer PTPE-g-beta-DK: under the nitrogen atmosphere, dissolving PTPE, beta-Ph and azodiisobutyronitrile in a dry DMSO solvent, carrying out polymerization reaction for 20-25 hours at 70-80 ℃, quenching the reaction with ice water after the reaction is finished, adding methyl tertiary butyl ether for precipitation, centrifugally purifying for three times, and carrying out vacuum drying to obtain a product poly (2- (4- (allyloxy) phenyl) ethylene-1, 2-tri) triphenyl-b-3- (4-vinylbenzyl) pentane-2, 4-dione PTPE-g-beta-DK; the mole ratio of PTPE to beta-Ph to azodiisobutyronitrile is 1:100:10;
(7) Synthesis of PTPE-g-beta-DK-Nd: dissolving PTPE-g-beta-DK in anhydrous ethyl acetate, stirring, adding an aqueous solution of neodymium acetate, stirring for 2-4 hours at room temperature, adding an anhydrous ethyl acetate solution of triphenylphosphine oxide, heating to 80 ℃, refluxing and stirring for 10-12 hours, cooling to room temperature after the reaction is ended, vacuum-filtering, washing with the anhydrous ethyl acetate, and vacuum-drying to obtain PTPE-g-beta-DK-Nd; the mol ratio of PTPE-g-beta-DK to neodymium acetate is 4:1-2:1; the molar ratio of PTPE-g-beta-DK to triphenylphosphine oxide is 2:1-1:1.
2. The method for preparing the near infrared two-zone 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 diphenyl ketone to the 4-hydroxy diphenyl ketone to the zinc powder is 1:1:4; the diphenyl ketone and TiCl 4 The molar ratio of (2) is 1:2-1:3.
3. The method for preparing the near infrared two-zone beta-diketone macromolecular rare earth complex with AIE activity according to claim 1, which is characterized in that: in step (2), the allyl bromide, TPE-OH and K 2 The molar ratio of CO is 1:1:1 to 1:2:2.
4. The method for preparing the near infrared two-zone 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 the near infrared two-zone 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; the molar ratio of the 3-mercaptopropionic acid to the benzyl bromide is 1:1.
6. The method for preparing the near infrared two-zone 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 azodiisobutyronitrile is 1:1:0.1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210575476.2A CN114853962B (en) | 2022-05-25 | 2022-05-25 | Preparation method of near infrared two-region beta-diketone macromolecular rare earth complex with AIE activity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210575476.2A CN114853962B (en) | 2022-05-25 | 2022-05-25 | Preparation method of near infrared two-region beta-diketone macromolecular rare earth complex with AIE activity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114853962A CN114853962A (en) | 2022-08-05 |
| CN114853962B true CN114853962B (en) | 2023-08-22 |
Family
ID=82639492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210575476.2A Active CN114853962B (en) | 2022-05-25 | 2022-05-25 | Preparation method of near infrared two-region beta-diketone macromolecular rare earth complex with AIE activity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114853962B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115974665B (en) * | 2023-01-29 | 2024-02-06 | 陕西科技大学 | Preparation method of oxygen-blocking AIE rare earth luminescent organic compound |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880343A (en) * | 2010-06-30 | 2010-11-10 | 广州市香港科大霍英东研究院 | Fluorescent polymer environment-friendly material with Beta-dione aggregative luminous structure |
| CN103254337A (en) * | 2013-05-07 | 2013-08-21 | 常州大学 | Beta-diketone rare earth complex and preparation method thereof |
| CN104177389A (en) * | 2014-09-03 | 2014-12-03 | 中国工程物理研究院化工材料研究所 | Rare-earth complex capable of being excited under different concentration conditions to generate high-efficiency rare-earth luminescence |
| CN106008192A (en) * | 2016-05-24 | 2016-10-12 | 南京工业大学 | Tetra-styryl diketone derivatives and application thereof |
| CN108559040A (en) * | 2018-05-08 | 2018-09-21 | 四川大学 | Polymer drug carrier, carrier micelle with redox response and AIE effects and preparation method thereof |
| CN108659154A (en) * | 2018-04-25 | 2018-10-16 | 西北师范大学 | The synthetic method of pH response type AIE fluorescence nano polymer quantum dots and application |
| CN108752512A (en) * | 2018-04-25 | 2018-11-06 | 西北师范大学 | Temperature response type AIE fluorescent polymers nano-particle and its synthetic method and application |
-
2022
- 2022-05-25 CN CN202210575476.2A patent/CN114853962B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880343A (en) * | 2010-06-30 | 2010-11-10 | 广州市香港科大霍英东研究院 | Fluorescent polymer environment-friendly material with Beta-dione aggregative luminous structure |
| CN103254337A (en) * | 2013-05-07 | 2013-08-21 | 常州大学 | Beta-diketone rare earth complex and preparation method thereof |
| CN104177389A (en) * | 2014-09-03 | 2014-12-03 | 中国工程物理研究院化工材料研究所 | Rare-earth complex capable of being excited under different concentration conditions to generate high-efficiency rare-earth luminescence |
| CN106008192A (en) * | 2016-05-24 | 2016-10-12 | 南京工业大学 | Tetra-styryl diketone derivatives and application thereof |
| CN108659154A (en) * | 2018-04-25 | 2018-10-16 | 西北师范大学 | The synthetic method of pH response type AIE fluorescence nano polymer quantum dots and application |
| CN108752512A (en) * | 2018-04-25 | 2018-11-06 | 西北师范大学 | Temperature response type AIE fluorescent polymers nano-particle and its synthetic method and application |
| CN108559040A (en) * | 2018-05-08 | 2018-09-21 | 四川大学 | Polymer drug carrier, carrier micelle with redox response and AIE effects and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114853962A (en) | 2022-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hoogenboom et al. | Synthesis of star-shaped poly (ε-caprolactone) via ‘click’chemistry and ‘supramolecular click’chemistry | |
| CN114853962B (en) | Preparation method of near infrared two-region beta-diketone macromolecular rare earth complex with AIE activity | |
| CN107325284B (en) | Hyperbranched polyphenyl triazole formate as well as preparation method and application thereof | |
| Hu et al. | The in situ “grafting from” approach for the synthesis of polymer brushes on upconversion nanoparticles via NIR-mediated RAFT polymerization | |
| Hou et al. | Polymer aggregates formed by polystyrene‐block‐poly (4‐vinyl‐pyridine) functionalized with rhenium (I) 2, 2′‐bipyridyl complexes | |
| JP2679010B2 (en) | Organic ferromagnet and manufacturing method thereof | |
| CN112979849B (en) | Method for catalyzing anionic polymerization of methyl methacrylate | |
| WO2008151499A1 (en) | Synthesis of acylarylenes and hyperbranched poly(acylarylene)s by metal-free cyclotrimerization of alkynes | |
| Pacini et al. | Clickable 2, 2‐bis (hydroxymethyl) propionic acid‐derived AB2 monomers: Hyperbranched polyesters through the CuAAC cycloaddition (click) reaction | |
| CN107722169B (en) | Macromolecular chain transfer agent containing coumarin fluorescent group and preparation method thereof | |
| JP7113509B2 (en) | Method for producing polymer metal complex | |
| JP2691014B2 (en) | Porphyrin aluminum complex | |
| JP2006335806A (en) | Method for producing low-molecular weight polyphenylene ether | |
| Archer et al. | A soluble linear Schiff-base coordination polymer containing eight-coordinate zirconium (IV) | |
| US11359049B2 (en) | Gold catalyzed polymerization reactions of unsaturated substrates | |
| Farah et al. | Synthesis and characterization of partially crosslinked poly (N-vinylcarbazole-vinylalcohol) copolymers with polypyridyl Ru (II) luminophores: Potential materials for electroluminescence | |
| CN110922418B (en) | Pyrrolo-pyrrole-dione conjugated oligomer, nanoparticle based on pyrrolo-pyrrole-dione conjugated oligomer and preparation methods of pyrrolo-pyrrole-dione conjugated oligomer and nanoparticle | |
| CN108191771A (en) | A kind of 3,4- dihydropyrimidine-2-ketos class function monomer and polymer and its their preparation method | |
| CN1313565C (en) | Rare earth/polymer composite luminous material and its preparation method | |
| CN115466392B (en) | Perylene bisimide cage polysilsesquioxane polymer material and preparation and fluorescence regulation method thereof | |
| Tsuchida et al. | Radical polymerization of metal‐coordinated monomers with ligands of pyrrole‐containing schiff bases | |
| EP0662485A2 (en) | Method of controlling the polymerization of acrylates | |
| RU2777171C1 (en) | Molecular polyfluorene brushes with polymethacrylic acid side chains | |
| KR102679412B1 (en) | Bismuth compounds, curable compositions and curing bodies | |
| CN115651098B (en) | Cucurbituril [7 ]/dithiocarbamic acid ester supermolecule combined RAFT chain transfer reagent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |