CN107619661B - Interface self-assembly rare earth complex supermolecule fluorescence/chiral nano composite material and preparation method thereof - Google Patents
Interface self-assembly rare earth complex supermolecule fluorescence/chiral nano composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a nanometer luminescent material technical field, in particular to an interface self-assembly rare earth complex supermolecule fluorescence/chirality nanometer composite material and a preparation method thereof, which firstly utilizes interface silanization and substitution reaction to form a single-layer film on the surface of nanometer silicon dioxide, and generates a nanometer complex with fluorescence characteristic through the coordination of a solid-liquid interface with rare earth inorganic salt, and secondly generates an organic-inorganic supermolecule nanometer material with fluorescence and supermolecule chirality double functions through the solid-liquid interface coordination between the nanometer complex and β -diketone ligand, bis (oxazoline) pyridine chiral ligand and tripyridine-cinchona chiral ligand.
Description
Technical Field
The invention belongs to the technical field of nano luminescent materials, and particularly relates to an interface self-assembly rare earth complex supermolecule fluorescence/chiral nano composite material and a preparation method thereof.
Technical Field
The molecular self-assembly technology from bottom to top is based on the structure and characteristics of single molecule or compound, through the non-covalent action between molecules, the supermolecule or nano composite material with special or multiple functions is designed and prepared, and the composite material is used to assemble molecular (nano) device, realizing the miniaturization and multiple functions of the product. The molecular self-assembly techniques mainly include: langmuir-blodgett (lb) film, self-assembled film, and layer-by-layer assembled film; the intermolecular forces on which they depend are generally van der waals forces, electrostatic interactions, hydrogen bonding, coordination, and the like.
Nano SiO2It is insoluble in water, except hydrofluoric acid, and is insoluble in common acid. Nano SiO2Has easily synthesized size/shapeEasy control, no toxicity, low price, easy surface modification, biocompatibility and the like, has the optical performance of resisting ultraviolet rays, and can improve the ageing resistance, strength and chemical resistance of other materials. In particular, nano SiO2The material has large specific surface area and high surface hydroxyl density, is easy to react with other functional groups to form a hybrid material, and has wide application prospect in many fields such as novel supramolecular materials, optics, medicines, heterogeneous catalysis and the like as an inorganic carrier material.
The luminescence of the rare earth complex is generated by the transition of 4f electrons of metal ions between different energy levels, and can emit electromagnetic radiation with various wavelengths from ultraviolet light, visible light to infrared light regions. The rare earth complex luminescent material has the following advantages: narrow luminous band (high color purity), strong light absorption capacity, high conversion efficiency, wide emission wavelength distribution region, long fluorescence lifetime and good stability.
In the invention, based on the design concept of molecular self-assembly, alkyl fatty amine is self-assembled to nano SiO by silanization2Forming a fatty amine monolayer modified nano SiO2(nanoSiO2NH2) Then leading the benzyl bromide or benzyl chloride group of the double or triple pyridine derivative to react with the nano SiO2The substitution reaction between the amino groups on the surface grafts the functional group of the di-or terpyridine to the nano SiO2Forming a double/triple pyridine single-layer film functionalized nano SiO2BPy or nanoSiO2TPy hybrid material. Thirdly, rare earth inorganic salt (LnX) is utilized3) With nano SiO2Interfacial coordination between bis/terpyridine films on surfaces to form nanoSiO2BPy@LnX3Or nanoSiO2TPy@LnX3Finally, β -diketone (β -dik) with good light absorption characteristic and polypyridine ligand with chiral functional group and nano SiO are utilized2BPy@LnX3Or nanoSiO2TPy@LnX3The coordination among the nanometer complexes forms a rare earth multi-element complex nanometer material with stronger red or green luminescence; with chiral polypyridine ligandsFormed nano SiO2The @ rare earth complex nano material has the characteristic of supermolecule chirality besides stronger rare earth ion characteristic fluorescence emission.
In the finally generated supermolecule nano composite material, bipyridyl, terpyridine, β -diketone and chiral polypyridine ligands are all good light absorption units, all of which can transfer absorbed light energy to an excited state energy level of rare earth ions through an intersystem crossing process and a ligand triplet state, and when excited electrons return to a ground state from the excited state of the rare earth ions, excited state energy is released in the form of fluorescence, so that fluorescence emission with specific rare earth metal ion characteristics is obtained.
In the invention, based on the design concept of molecular self-assembly, alkyl fatty amine is self-assembled to nano SiO by silanization reaction2The surface of the nano SiO modified by the fatty amine single-layer film is formed2(nanoSiO2NH2) Then leading the benzyl bromide or benzyl chloride group of the double or triple pyridine derivative to react with the nano SiO2The substitution reaction between the amino groups on the surface grafts the functional group of the di-or terpyridine to the nano SiO2Forming a double/triple pyridine single-layer film functionalized nano SiO2BPy or nanoSiO2TPy hybrid material. Thirdly, rare earth inorganic salt (LnX) is utilized3) With nano SiO2Interfacial coordination between bis/terpyridine films on surfaces to form nanoSiO2BPy@LnX3Or nanoSiO2TPy@LnX3Finally, β -diketone (β -dik) with good light absorption characteristic and polypyridine ligand with chiral functional group and nano SiO are utilized2BPy@LnX3Or nanoSiO2TPy@LnX3The coordination among the nanometer complexes forms a rare earth multi-element complex nanometer material with stronger red or green luminescence; nano SiO formed with chiral polypyridine ligand2@ rare earth complexThe nano material has the characteristic of supermolecule chirality besides stronger fluorescence emission of rare earth ions.
In the finally generated supermolecule nano composite material, bipyridyl, terpyridine, β -diketone and chiral polypyridine ligands are all good light absorption units, all of which can transfer absorbed light energy to an excited state energy level of rare earth ions through an intersystem crossing process and a ligand triplet state, and when excited electrons return to a ground state from the excited state of the rare earth ions, excited state energy is released in the form of fluorescence, so that fluorescence emission with specific rare earth metal ion characteristics is obtained.
Disclosure of Invention
The invention aims to provide an interface self-assembly rare earth complex supermolecule fluorescence/chiral nano composite material which is simple to prepare and environment-friendly and a preparation method thereof.
The interface self-assembly rare earth complex supramolecular fluorescence/chiral nano composite material provided by the invention is an organic-inorganic (chiral) supramolecular nano composite material with strong rare earth fluorescence emission, and is formed by silanization reaction and intermolecular coordination from bottom to top on a solid-liquid interface, wherein precursor materials of the material are nano silicon dioxide, rare earth inorganic salt, bipyridyl (BPy), terpyridine (TPy), β -diketone (β -dik), bis (oxazoline) pyridine (R-pybox, S-pybox) and terpyridine-quinine (TPyCCD, TPyCCN) derivatives.
The chemical structures of rare earth triflate, bipyridine, terpyridine, and β -dione in the precursor material are shown below:
chiral polypyridine derivatives in the precursor material: the chemical structures of the tri-pyridine-cinchonine (TPyCCD, TPyCCN) and the chiral bis (oxazolinyl) pyridine (R-pybox, S-pybox) are shown as follows:
the invention provides a preparation method of an interface self-assembly rare earth complex supramolecular fluorescence/chiral nano composite material, which comprises the following specific steps:
firstly, utilizing interface self-assembly method to prepare nano silicon dioxide (nano SiO)2) The surface of the nano-scale organic-inorganic hybrid material is grafted with a single-layer film consisting of bipyridyl (BPy) or terpyridyl (TPy) derivatives to form a high-stability nano-organic-inorganic hybrid material which is marked as nano SiO2BPy and nanoSiO2Tpy; further with rare earth inorganic salts (LnX)3) The coordination of the solid-liquid interface generates a complex with the fluorescent characteristic, which is marked as nano SiO2BPy@LnX3And nanoSiO2TPy@LnX3；
(II) through nano complex nano SiO2BPy@LnX3Or nanoSiO2TPy@LnX3The rare earth binary complex supermolecule nano composite material is formed by the interface coordination between the rare earth binary complex and β -diketone ligand (β -dik), and is marked as nano SiO2BPy@Ln(β-dik)nAnd nanoSiO2TPy@Ln(β-dik)n；
(III) through nano complex nano SiO2BPy@LnX3Or nanoSiO2TPy@LnX3The rare earth binary complex chiral supermolecule nano composite material is formed by the interface coordination between the rare earth binary complex and chiral polypyridine ligand bis (oxazolinyl) pyridine (i-pybox) and terpyridine-cinchonine (i-TPyCCX), and is marked as nano SiO2BPy @ Ln (i-pybox) and nanoSiO2TPy@Ln(i-TPyCCX)。
In the invention, the operation flow of the step (I) is as follows:
firstly, nano SiO with hydrophilized surface2Dispersing in methanol-DMF mixed solvent (volume ratio is 1:0.5-1:2), adding 5-10% of 3-aminopropyltrimethoxysilane by mass percent, and stirring and reacting in a water bath or oil bath reactor at 60-80 ℃ for 24-48 hours. ColdCooling to room temperature, performing centrifugal separation at 3000-6000rpm, fully washing with methanol, removing unreacted 3-aminopropyl trimethoxy silane, and obtaining aminated nano SiO2；
Secondly, aminated nano SiO2Further stirring and reacting with benzyl bromide or benzyl chlorinated bis/terpyridine with the mass ratio of 5-10% in a water bath or oil bath reactor with the temperature of 60-80 ℃ in a methanol-DMF mixed solvent for 5-10 hours; cooling to room temperature, carrying out centrifugal separation at 3000-6000rpm, fully washing with methanol, removing unreacted organic matters, and generating the single-layer film modified nano SiO of the double/terpyridine ligand derivative2Organic-inorganic hybrid materials, i.e. nanoSiO2BPy and nanoSiO2Tpy；
Finally, nanoSiO2BPy and nanoSiO2TPy hybrid material and 5-10% of rare earth inorganic salt LnX by mass3Dissolving in methanol-DMF mixed solvent, stirring and reacting for 24-72 hours at room temperature, centrifuging at 3000-6000rpm, washing with methanol sufficiently to remove unreacted rare earth inorganic salt to obtain the rare earth fluorescent nano complex nanosilicon dioxide2BPy@LnX3And nanoSiO2TPy@LnX3。
Wherein, the NanoSiO2BPy or nanoSiO2TPy concentration of 10-50 mg/mL, rare earth inorganic salt LnX3The concentration of (b) is 1-5 mg/mL.
In the invention, the operation flow of the step (II) is as follows:
mixing the rare earth nano complex with nano SiO2BPy@LnX3Or nanoSiO2TPy@LnX3Dispersing in methanol-DMF mixed solution, adding β -diketone anion i-TPyCCX methanol solution (namely β -diketone and KOH methanol solution with the molar ratio of 1:1-1: 1.05) with the mass ratio of 5-10% while stirring, continuing stirring at room temperature for reaction for 24-72 hours, centrifugally separating at 3000-6000rpm, fully washing with methanol, removing unreacted β -diketone anion to obtain the nano SiO2BPy@Ln(β-dik)nAnd nanoSiO2TPy@Ln(β-dik)nSupramolecular nanocomposites.
Wherein, the NanoSiO2BPy@LnX3And nanoSiO2TPy@LnX3The concentration of (a) is 10-50 mg/mL, and the concentration of β -diketone anion i-TPyCCX is 1-5 mg/mL.
In the invention, the operation flow of the step (three) is as follows:
mixing the rare earth nano complex with nano SiO2BPy@LnX3Or nanoSiO2TPy@LnX3Dispersing in chloroform-DMF mixed solution, adding chloroform-DMF solution of chiral polypyridine derivative i-pybox in the mass ratio of 5-10% while stirring, stirring at room temperature for reaction for 24-72 hr, centrifuging at 3000-6000rpm, washing with chloroform and methanol to eliminate unreacted chiral polypyridine and obtain nanometer SiO with both fluorescent and supermolecular chiral functions2BPy @ Ln (i-pybox) and nanoSiO2TPy @ Ln (i-TPyCCX) nanocomposites.
Wherein, the NanoSiO2BPy@LnX3And nanoSiO2TPy@LnX3The concentration of the chiral polypyridine derivative i-pybox is 10-50 mg/mL, and the concentration of the chiral polypyridine derivative i-pybox is 1-5 mg/mL.
The invention provides a method for preparing a rare earth complex nano fluorescent material by utilizing a molecular assembly technology. Wherein, the double/terpyridyl monofilm is prepared by a self-assembly film-based method through nanometer SiO2A 'nano-scale' ligand is generated by the silanization reaction of the surface, and then the nano-scale ligand and rare earth triflate or nitrate are subjected to interface coordination reaction to generate the nano SiO with fluorescence characteristic2BPy@LnX3Or nanoSiO2TPy@LnX3A nano-complex. Although these nanocomplexes already have luminescent properties, the smaller anion X is not saturated in coordination number of the rare earth ion−Therefore, the invention further forms the nanoSiO with stronger light absorption capacity and hydrophobic characteristic by the coordination reaction of the rare earth metal ions and β -diketone or chiral polypyridine ligand through the coordination action between the two ligands on the solid surface2BPy@Ln(β-dik)nAnd nanoSiO2TPy@Ln(β-dik)nSupermolecule nano composite material and nano SiO with double functions of fluorescence and supermolecule chirality2BPy @ Ln (i-pybox) and nanoSiO2TPy @ Ln (i-TPyCCX) nanocomposites.
The supermolecule fluorescent nano material prepared by the invention not only has the basic characteristics of a rare earth complex luminescent material, namely strong fluorescence emission, good monochromaticity (narrow half-peak width), long fluorescence service life, no interference of environmental factors and the like, but also has the characteristics of large specific surface area, easy purification and separation and the like of the nano material. The nano composite material containing the chiral ligand also has the characteristic of supermolecule chiral material generated by ligand chiral induction. The nano composite materials can be used for the fields of developing novel nano fluorescent materials/nano fluorescent devices, fluorescent markers, medicine marking and tracking, fluorescent imaging of cell/tissue/small animal biological systems and the like.
The invention is based on the interface molecule self-assembly technology, and the rare earth complex is fixed on the nano SiO in the form of an object (film)2Has the following advantages:
(1) because the nano fluorescent material is based on nano SiO with high specific surface area, good mechanical strength, biocompatibility and low price2And the complex is formed by coordination bonds with the rare earth complex, so that the composite material has higher thermal and chemical stability.
(2) The preparation of the nano composite materials is based on the basic principle of molecular engineering and is gradually generated by adopting a bottom-up method, so that the composition and the distribution of the composite materials have molecular level controllability and selectivity.
(3) Because the composite materials are solid nano SiO2Is formed for the carrier and is connected by covalent bonds and coordinate bonds, thus being easy to purify and separate by a centrifugal method.
(4) Due to the nanometer SiO2The size of the carrier is controlled within the range of 10-20 nm, the polypyridine and β -diketone with different absorption wavelengths are adopted as the multi-element ligand, and the different absorption wavelengths of the ligands provide the possibility of adjusting the excitation wavelength and are more suitable for medicinesFluorescence imaging of biological systems such as biomarkers, cells/tissues/small animals.
In a word, the preparation process of the method is simple and easy to implement, has low requirements on equipment and production environment, is environment-friendly, and can simply realize the regulation and control of the components and the spatial structure of the molecular material.
In the invention, the self-assembly of all parts except the first self-assembly monolayer film is finished in a water bath or an oil bath at 60 ℃, and the self-assembly of all parts is carried out at room temperature. The separation of the solid product is carried out by a centrifuge and sufficiently washed with the reaction solvent without requiring a special reaction apparatus.
Drawings
FIG. 1 illustrates the formation of bipyridine monolayer film and its reaction with rare earth triflate to form nanoSiO using 2, 2' -bipyridine and DBM as examples2BPy@Ln(CF3SO3)3Nano complex and reaction with DBM to produce nano SiO2BPy@Ln(DBM)3The process of supramolecular nanocomposites.
FIG. 2 illustrates the formation of a single layer terpyridine film and its reaction with a rare earth inorganic salt to form nanoSiO using terpyridine, TPyCCN and R-pybox as examples2TPy @ Ln (i-TPyCCN) and nanoSiO2TPy @ Ln (R-pybox) supramolecular chiral nanocomposites.
FIG. 3 is a view of a nanocomposite, nanoSiO2BPy@Eu(DBM)nPhotographs of (a) before and (B) after centrifugation dispersed in a methanol solution; and nanoSiO2BPy@Eu(CF3SO3)3And nanoSiO2BPy@Eu(DBM)nPhotographs of the solid powder at different excitation wavelengths, (C) excitation wavelength 300 nm and (D) excitation wavelength 365 nm.
Detailed Description
The invention is further described below by way of examples.
Example 1:
taking 20 g of nano SiO with the content of 40 percent2Dispersing in 300 mL of methanol-DMF mixed solvent (volume ratio 1:1), adding 1 g of methanol-DMF solution (20 mL) of 3-aminopropyltrimethoxysilane, and heating in 60 deg.C water bath or oilThe reaction was stirred in the bath reactor for 2 days. Cooling to room temperature, centrifuging at 4000rpm, washing with methanol thoroughly to remove unreacted 3-aminopropyltrimethoxysilane to obtain white aminated nanometer SiO2The aminated nano SiO2The surface amino group content is about 5.3%.
Taking 5 g of aminated nano SiO2Dispersing in 150 mL of methanol-DMF mixed solvent (volume ratio 1:1), adding 0.2 g of 4,4 '-dimethylchloro-2, 2' -bipyridine (dissolved in 10 mL of methanol-DMF mixed solvent) in mass ratio, and stirring in a water bath or oil bath reactor at 60 ℃ for reaction for 10 hours. Cooling to room temperature, centrifuging at 4000rpm, and washing with methanol to obtain light yellow nanometer SiO modified with 2, 2' -bipyridine ligand single-layer film2I.e. nanoSiO2BPy. Modified nano SiO2The surface organic content is about 8.5%, and the substance is insoluble in organic solvents such as water and methanol, but can be uniformly dispersed in solvents such as DMF.
Taking 2 g of nanoSiO2BPy was dispersed in 50 mL of methanol-DMF, and 0.1 g of a methanol-DMF solution (10 mL) of europium trifluorosulfonate was added to stir the reaction at room temperature for 2 days. Centrifugally separating at 4000rpm, and fully washing with methanol to obtain milky white nano complex nanoSiO2BPy@Eu(CF3SO3)3. The content of inorganic and organic matters modified on the surface of the material is about 10.2 percent, the material is insoluble in organic solvents such as water, methanol and the like, but can be uniformly dispersed in solvents such as DMF and the like, the material has the characteristic absorption of bipyridyl at 285 nm and has stronger rare earth Eu in the range of 580-720 nm3+Red fluorescence emission of the ion, with 614 nm being the strongest emission peak.
Example 2:
2 g of nanoSiO2BPy@Eu(CF3SO3)3The nano complex is dispersed in a methanol-DMF mixed solution, and a Dibenzoylmethane (DBM) anionic methanol solution (a mixed solution of 0.2 g of DBM and 0.05 g of KOH) with a mass ratio of about 10% is added with stirring. The reaction was continued for 2 days with stirring at room temperature, centrifuged at 4000rpm, and sufficiently washed with methanol to remove unreacted DBM, thereby obtaining milky-white nanoSiO2BPy@Eu(DBM)3A nanocomposite material. The content of inorganic complexes and organic matters modified on the surface of the material is about 10 percent, the inorganic complexes and the organic matters are insoluble in organic solvents such as water, methanol and the like, but can be uniformly dispersed in solvents such as DMF and the like, the material has the characteristic absorption of bipyridyl at 285 nm and has stronger rare earth Eu in the range of 580-720 nm3+Ionic red fluorescence emission with 613 nm being the strongest emission peak.
Example 3:
2 g of nanoSiO2BPy@Eu(CF3SO3)3The nanocomplex was dispersed in 50 mL of a chloroform-DMF mixed solvent, and 10 mL of a chloroform-DMF solution containing 0.2 g of TPyCCN was added with stirring. The reaction was continued for 2 days with stirring at room temperature, centrifuged at 4000rpm, and sufficiently washed with chloroform and methanol to remove unreacted TPyCCN, thereby obtaining pale yellow nanoSiO2BPy @ Eu (TPyCCN) supramolecular chiral nanocomposite. The content of inorganic complexes and organic matters on the surface of the composite material is about 10 percent, the composite material is insoluble in organic solvents such as water, methanol and the like, but can be uniformly dispersed in solvents such as DMF and the like, tests show that the material has the characteristic absorption of bipyridyl and terpyridyl at the position of 285-310 nm, and has stronger rare earth Eu within the range of 570-720 nm3+Ionic red fluorescence emission with 614 nm being the strongest emission peak. Circular dichroism spectrum shows that the supermolecular material has chiral property.
Example 4:
2 g of nanoSiO2BPy@Eu(CF3SO3)3The nanocomplex was dispersed in 50 mL of chloroform-DMF mixed solution, and 10 mL of chloroform-DMF solution containing 0.2 g R-pybox was added with stirring. The reaction was continued for 2 days with stirring at room temperature, centrifuged at 4000rpm, and washed thoroughly with methanol to remove unreacted R-pybox, to give pale yellow nanoSiO2BPy @ Eu (R-pybox) supramolecular chiral nanocomposite. The content of inorganic complexes and organic matters on the surface of the composite material is about 10 percent, the composite material is insoluble in organic solvents such as water, methanol and the like, but can be uniformly dispersed in solvents such as DMF and the like, tests show that the material has the characteristic absorption of bipyridyl and terpyridyl at the position of 285-310 nm, and has stronger rare earth Eu within the range of 570-720 nm3+Ionic red fluorescence emission with 614 nm being the strongest emission peak. Circular dichroism spectrum shows that the supermolecular material has chiral property.
Claims (8)
1. A preparation method of an interface self-assembly rare earth complex supramolecular fluorescence/chiral nano composite material is characterized by comprising the following specific steps:
grafting a single-layer film consisting of bipyridine or terpyridine derivatives on the surface of nano silicon dioxide by using an interface self-assembly method to form a high-stability nano organic-inorganic hybrid material marked as nano SiO2BPy and nanoSiO2TPy, respectively; further with rare earth triflates: LnX3The coordination of the solid-liquid interface generates a complex with the fluorescent characteristic, which is marked as nano SiO2BPy@LnX3And nanoSiO2TPy@LnX3(ii) a Here, the rare earth Ln is Eu or Tb, the same applies below;
(II) through nano complex nano SiO2BPy@LnX3Or nanoSiO2TPy@LnX3The rare earth binary complex supermolecule nano composite material is formed by the interface coordination between the rare earth binary complex and β -diketone ligand and is marked as nano SiO2BPy@Ln(β-dik)nAnd nanoSiO2TPy@Ln(β-dik)n，n = 1−3；
(III) through nano complex nano SiO2BPy@LnX3Or nanoSiO2TPy@LnX3The rare earth binary complex chiral supermolecule nano composite material is formed by the interface coordination between the rare earth binary complex and the chiral polypyridine ligand bis (oxazoline) pyridine and the tripyridine-cinchonine, and is marked as nano SiO2BPy @ Ln (i-pybox) and nanoSiO2TPy@Ln(i-TPyCCX)。
2. The method according to claim 1, wherein the operation procedure of step (one) is as follows:
firstly, nano SiO with hydrophilized surface2Dispersing in methanol-DMF mixed solvent, adding 5-10% by mass of 3-aminopropyltrimethoxysilane, stirring in 60-80 deg.C water bath or oil bath reactorReacting for 24-48 hours; cooling to room temperature, centrifuging at 3000-6000rpm, washing with methanol, removing unreacted 3-aminopropyl trimethoxy silane to obtain aminated nanometer SiO2；
Secondly, aminated nano SiO2Further stirring and reacting with benzyl bromide or benzyl chlorinated bis/terpyridine with the mass ratio of 5-10% in a water bath or oil bath reactor with the temperature of 60-80 ℃ in a methanol-DMF mixed solvent for 5-10 hours; cooling to room temperature, carrying out centrifugal separation at 3000-6000rpm, fully washing with methanol, removing unreacted organic matters, and generating the single-layer film modified nano SiO of the double/terpyridine ligand derivative2Organic-inorganic hybrid materials, i.e. nanoSiO2BPy and nanoSiO2TPy；
Finally, nanoSiO2BPy and nanoSiO2TPy hybrid material and 5-10% by mass of rare earth triflate LnX3Dissolving in methanol-DMF mixed solvent, stirring and reacting for 24-72 hours at room temperature, centrifuging at 3000-6000rpm, washing with methanol sufficiently to remove unreacted rare earth triflate, and obtaining the nano complex nanosilicon dioxide with rare earth fluorescence2BPy@LnX3And nanoSiO2TPy@LnX3。
3. The method according to claim 2, wherein the nanoSiO is2BPy or nanoSiO2TPy concentration of 10-50 mg/mL, rare earth triflate LnX3The concentration of (b) is 1-5 mg/mL.
4. The preparation method according to claim 2 or 3, wherein the operation flow of the step (II) is as follows:
mixing the rare earth nano complex with nano SiO2BPy@LnX3Or nanoSiO2TPy@LnX3Dispersing in methanol-DMF mixed solution, adding 5-10% methanol solution of β -diketone anion by mass ratio while stirring, continuing stirring at room temperature for reaction for 24-72 hours, centrifuging at 3000-6000rpm, washing fully with methanol to remove unreacted β -diketone anion to obtain the nano SiO2BPy@Ln(β-dik)nAnd nanoSiO2TPy@Ln(β-dik)nSupramolecular nanocomposites.
5. The method according to claim 4, wherein the NanoSiO is a NanoSiO2BPy@LnX3And nanoSiO2TPy@LnX3The concentration of (b) is 10-50 mg/mL, and the concentration of β -diketone anion is 1-5 mg/mL.
6. The preparation method according to claim 2 or 5, wherein the operation flow of the step (three) is as follows:
mixing the rare earth nano complex with nano SiO2BPy@LnX3Or nanoSiO2TPy@LnX3Dispersing in chloroform-DMF mixed solution, adding chloroform-DMF solution of chiral polypyridine derivative i-TPyCCX with the mass ratio of 5-10% while stirring, continuing to stir at room temperature for reaction for 24-72 hours, centrifugally separating at 3000-6000rpm, fully washing with chloroform and methanol, removing unreacted chiral polypyridine to obtain the nano SiO with dual functions of fluorescence and supermolecular chirality2BPy @ Ln (i-pybox) and nanoSiO2TPy @ Ln (i-TPyCCX) nanocomposites.
7. The method according to claim 6, wherein the NanoSiO is a NanoSiO2BPy@LnX3And nanoSiO2TPy@LnX3The concentration of the chiral polypyridine derivative i-TPyCCX is 10-50 mg/mL, and the concentration of the chiral polypyridine derivative i-TPyCCX is 1-5 mg/mL.
8. Interface self-assembly rare earth complex supermolecular fluorescence/chiral nano composite material marked as nano SiO prepared by the preparation method of any one of claims 1 to 72BPy@Ln(β-dik)nOr nanoSiO2TPy@Ln(β-dik)n，n =1-3。
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