Adjustable lanthanide series supramolecular cascade panchromatic light-emitting assembly material as well as preparation method and application of adjustable lanthanide series supramolecular cascade panchromatic light-emitting assembly material

Abstract

The invention provides an adjustable lanthanide series supramolecular cascade panchromatic light-emitting assembly material as well as a preparation method and application thereof, an adjustable lanthanide series supramolecular cascade full-spectrum light-emitting system is constructed by co-assembling an organic antenna molecule / lanthanide series ion complex, hectorite, Nile blue / Nile red and rhodamine 800 (Rh800), the energy transfer efficiency is high, and the material is suitable for large-scale production. And full-spectrum adjustable light emission can be realized. The assembly can be used as intelligent anti-counterfeiting ink, and multi-layer information encryption is realized through multi-color light-emitting coding.

Description

Technical Field

[0001] This invention relates to the field of intelligent luminescent materials technology, and in particular to a tunable lanthanide supramolecular cascade full-color luminescent assembly material, its preparation method, and its application. Background Technology

[0002] Currently, supramolecular cascade assembly can achieve cascade energy transfer, thereby realizing multicolor and near-infrared luminescence, which is a current research hotspot and has wide applications in information encryption, cell imaging, and catalysis. Utilizing cascade assembly through hydrogen-bonded host-guest interactions, π-π stacking, hydrophobicity, and electrostatic effects can not only alter the topological structure of the assembly and improve its luminescence performance, but also endow the system with dynamic reversibility and multiple stimulus-response capabilities. However, existing supramolecular cascade assemblies suffer from low energy transfer efficiency and difficulty in achieving full-spectrum tunable luminescence. Summary of the Invention

[0003] In view of the problems existing in the prior art, the present invention provides a tunable lanthanide supramolecular cascade full-color luminescent assembly material, its preparation method, and its application. The assembly material has high energy transfer efficiency and can achieve tunable luminescence across the entire spectrum.

[0004] Specifically, the first aspect of the present invention provides a tunable lanthanide supramolecular cascade full-color luminescent assembly material, comprising:

[0005] The donor comprises a host and a guest, wherein the host is lithium saponite and the guest is an organic antenna molecule / lanthanide ion complex; the host and the guest form an assembly through host-guest interactions;

[0006] The receptor comprises a first dye and a second dye, wherein the first dye comprises either Nile Blue or Nile Red, and the second dye comprises Rh800.

[0007] This invention constructs a tunable lanthanide supramolecular cascade full-spectrum luminescence system by co-assembling organic antenna molecules / lanthanide ion complexes, lithium saponite (LP), Nile blue / Nile red (NR / NB), and Rhodamine 800 (Rh800). This system not only exhibits light-trapping cascade energy transfer from optically tunable rare elements to NB (energy transfer efficiency up to 58%) or NR (energy transfer efficiency up to 75%), and then to Rh800 (energy transfer efficiency exceeding 20%), but also achieves an ultra-large Stokes shift exceeding 600 nm and demonstrates acid-base tunable assembly and disassembly capabilities. In particular, the electrostatic interaction between LP and the organic antenna molecules effectively promotes the green luminescence of lanthanide ions and the blue luminescence of the organic antenna molecules. Notably, this lanthanide supramolecular assembly utilizes multi-component cascade energy transfer to create a powerful information security platform. By adjusting the donor and acceptor ratios, full-spectrum tunable luminescence from blue to green, red, and near-infrared light is achieved. This unique feature enables it to function as a multi-functional writing ink, facilitating switchable data logic encryption, anti-counterfeiting for multi-color information, embedding complex data in multi-color patterns and accurately reading it out with simple reading, encoding information in ASCII format, and providing a convenient and efficient method for information storage and retrieval while ensuring a high level of security.

[0008] In some embodiments, the organic antenna molecule includes G1, which has the following structural formula:

[0009] In some embodiments, the lanthanide ions include Tb 3+ 、Tb 4+ Eu 3+ At least one of them.

[0010] In some embodiments, the mass ratio of the object to the subject is 0.001:(0.1-3), preferably 0.001:(0.1-1).

[0011] In some embodiments, the molar ratio of lanthanide ions to the first dye is 1:1 or more, preferably 3:1-16:1; the molar ratio of the first dye to the second dye is 0.1:1 or more, preferably 0.1:1-6:1.

[0012] In some embodiments, the molar ratio of lanthanide ions to organic antenna molecules is 0.2:1 to 0.6:1.

[0013] A second aspect of the present invention provides a method for preparing the tunable lanthanide supramolecular cascade full-color luminescent assembly material of the first aspect of the present invention, comprising the following steps:

[0014] Preparation of organic antenna molecule / lanthanide ion complexes;

[0015] The tunable lanthanide supramolecular cascade full-color luminescent assembly material can be obtained by co-assembling the organic antenna molecule / lanthanide ion complex, lithium saponite, the first dye, and the second dye.

[0016] The preparation method of this invention is simple, the conditions are mild, and it is highly reproducible, making it suitable for large-scale promotion.

[0017] In some embodiments, the preparation of the organic antenna molecule / lanthanide ion complex includes: mixing the organic antenna molecule with a salt containing lanthanide ions in water to obtain an organic antenna molecule / lanthanide ion complex solution.

[0018] In some embodiments, the salt containing lanthanide ions includes one or more of water-soluble nitrates, water-soluble sulfates, and water-soluble hydrochlorides.

[0019] In some embodiments, co-assembling the organic antenna molecule / lanthanide ion complex, lithium saponite, first dye, and second dye includes:

[0020] Lithium saponite was added to the organic antenna molecule / lanthanide ion complex solution, and the mixture was then used to obtain the donor solution.

[0021] A first dye is added to the donor solution, and after mixing, a second dye is added.

[0022] The third aspect of this invention provides an application of the tunable lanthanide supramolecular cascade full-color luminescent assembly material of the first aspect of this invention in smart logic gate anti-counterfeiting materials.

[0023] The following is an explanation and description of the terminology used in this invention:

[0024] Lithium saponite LP: Full name is lithium magnesium silicate It is a synthetically produced lithium magnesium silicate clay with a unique layered structure and excellent physicochemical properties. Its chemical formula is [Mg...]. 5.34 Li 0.66 Si8O 20 [OH)4]Na 0.66 It has a layered structure, consisting of two tetrahedral silica layers sandwiching an octahedral magnesium ion layer. The magnesium ions can be partially replaced by lithium ions, making the surface negatively charged. Individual nanosheets have a diameter of approximately 25–30 nm and a thickness of approximately 1 nm. After being dispersed in water, it exhibits a significant negative surface charge, enabling it to bind with various molecules while maintaining a certain degree of stability.

[0025] The structure of naftimidazole pyridine carboxylic acid (G1) is as follows:

[0026] Nile Red (NR) has the following structural formula:

[0027] Nile Blue (NB) has the following structural formula:

[0028] Rhodamine (Rh800) has the following structural formula:

[0029] The beneficial effects of this invention are:

[0030] 1. By constructing a lanthanide supramolecular cascade assembly, multi-level energy transfer from the ultraviolet to the near-infrared region was achieved, with energy transfer efficiencies as high as 58% (Nile Blue) and 75% (Nile Red). The final transfer efficiency to Rh800 exceeded 20%, exhibiting an ultra-large Stokes shift (>600 nm). This highly efficient energy transfer system provides a new approach for long-wavelength near-infrared luminescence.

[0031] 2. By precisely adjusting the donor By adjusting the ratio of the receptor (Nile Blue / Nile Red, Rh800), tunable emission across the entire spectrum from blue to green, red, and near-infrared light was achieved. In particular, at specific ratios, the assembly was able to emit light close to standard white light (CIE coordinates (0.31, 0.33), enabling multicolor display and lighting applications.

[0032] 3. The assemblies exhibit dynamic responses to pH and light stimulation. For example, acid-base regulation can reversibly control the dissociation and recombination of the assemblies, enabling them to adapt to complex environments.

[0033] 4. The addition of lithium saponite promotes the luminescence of lanthanide ions (luminescence enhancement by 18.7 times, quantum yield increase by 5.7 times, and lifetime increase by 6.9 times). This enhancement effect provides a new approach for the development of rare earth luminescent materials.

[0034] 5. The assembly of this invention can be used as intelligent anti-counterfeiting ink, achieving multi-level information encryption through multi-color luminescent coding. Combining logic gate design and ASCII encoding technology, complex information can be embedded in multi-color patterns and read through simple scanning, offering both high security and convenience. For example, the classical poem "Ascending the Stork Tower" was successfully encrypted into a multi-color microarray and decrypted under specific conditions. Attached Figure Description

[0035] Figure 1 This is the hydrogen NMR spectrum of G1.

[0036] Figure 2Test patterns provided for some embodiments of the present invention: (a) absorption spectrum of LP (from 0 wt% to 3 wt%) added to aqueous solution of G1 (0.02 mM) at 298 K; (b) transient and steady-state fluorescence spectra (λex = 254 nm) of LP (from 0 wt% to 3 wt%) added to aqueous solution of G1 (0.02 mM) at 298 K; (c) ultraviolet absorption spectrum of Tb (1 eq) added to aqueous solution of G1 (0.02 mM) at 298 K; (d) transient and steady-state fluorescence spectra (λex = 254 nm) of Tb (3 / 5 eq) added to aqueous solution of G1 (0.02 mM) at 298 K.

[0037] Figure 3 Test graph provided for some embodiments of the present invention: emission intensity variation at 545nm and Tb 3+ Relationship of G1 molar ratio (λex=254nm).

[0038] Figure 4 Test patterns provided for some embodiments of this application: (a) absorption spectrum with added LP; (b) pure water, G1 / Tb complex, and Transmittance at 400 nm and the corresponding Tyndall effect in aqueous solution (inset); (c) The G1 / Tb complex and its corresponding Tyndall effect were investigated by fluorescence spectroscopy. Fluorescence spectra of G1 / Tb complexes at 298 K; (d) fluorescence spectra of G1 / Tb complexes and Fluorescence lifetime decay curve at 545 nm.

[0039] Figure 5 Transmission electron microscopy (TEM) images: (a) G1, (b) G1 / Tb complex. and

[0040] Figure 6 Test diagrams provided for some embodiments of this application: (a) G1, (b) G1 / Tb complex, (c) and (d) In an aqueous solution at 298 K (G1 concentration of 0.02 mM, Tb 3+ The zeta potential at a concentration of 0.0067 mM and a mass fraction of LP of 0.3 wt%.

[0041] Figure 7 Test diagrams provided for some embodiments of this application: (a) Normalized absorption spectrum and transient steady-state fluorescence spectrum of NR and (a) Transient and steady-state fluorescence spectra of the assembly; (b) Different D / A molar ratios (c) Transient and steady-state fluorescence spectra in aqueous solution; Energy transfer efficiency in aqueous solution; (d) Normalized absorption spectrum and transient steady-state fluorescence spectrum of NB and (e) Transient and steady-state fluorescence spectra of the assembly in aqueous solution; Transient and steady-state fluorescence spectra in aqueous solution; (f) Different D / A molar ratios Energy transfer efficiency in aqueous solution.

[0042] Figure 8 Test patterns provided for some embodiments of this application: (a) Normalized absorption spectrum and transient steady-state fluorescence spectrum of Rh800 and (a) Transient and steady-state fluorescence spectra of the assembly; (b) Different D / A molar ratios Transient and steady-state fluorescence spectra in aqueous solution; effects of different concentrations of Rh800 on... The effect of energy transfer efficiency; (c) in aqueous solution; (d) normalized absorption spectrum and transient steady-state fluorescence spectrum of Rh800, and Transient and steady-state fluorescence spectra of the assembly in aqueous solution; (e) Transient and steady-state fluorescence spectra at different D / A molar ratios; (f) Effects of different concentrations of Rh800 in aqueous solution on... The effect of luminescence efficiency; (g) transient and steady-state fluorescence spectra from blue to green; (h) transient and steady-state fluorescence spectra from green to red; (i) CIE chromaticity diagram of panchromatic emission; (j) possible working mechanism of energy transfer process.

[0043] Figure 9 Test diagrams provided for some embodiments of this application: (a) SIR, (b) RhB and (c) Rh800 added at different concentrations Fluorescence spectra of the assemblies at 298 K; and the corresponding co-assembly energy transfer efficiencies: (d) SIR, (e) RhB and (f) Rh800 (G1 concentration 0.02 mM, LP mass fraction 0.3 wt%, SIR, RhB and Rh800 concentrations 0.006 mM, λex = 254 nm).

[0044] Figure 10 Test images provided for some embodiments of this application: (a) a schematic diagram of text encoded with fluorescent colors; (b) a photograph of multi-level information storage using supramolecular ink under 254nm irradiation; (c) using on a smartphone platform. and The operating steps of the RGB analysis and calculation application, and the addition of different concentrations of NR and Rh800. Photographs of R, G, B, and R / G values ​​under 254nm illumination.

[0045] Figure 11 Based on The combinational logic gate system of the component's emission color and its corresponding truth table (A represents the white light output of the logic gate).

[0046] Figure 12 This is a diagram showing the conversion from binary to character.

[0047] Figure 13 This is a diagram showing the conversion from binary to hexadecimal. Detailed Implementation

[0048] To better understand the technical solution of this application, the embodiments of this application will be described in detail below with reference to the accompanying drawings.

[0049] It should be understood that the described embodiments are merely some, not all, of the embodiments in this application. All other embodiments obtained by those skilled in the art based on the embodiments in this application without inventive effort are within the scope of protection of this application.

[0050] Unless otherwise expressly stated otherwise, all scopes referenced in this application include end values.

[0051] The terms “a” or “an” are used in this application to describe the elements and components described herein. This is done solely for convenience and to provide a general meaning for the scope of this application. Such a description should be understood to include one or at least one, and the singular includes the plural, unless clearly otherwise indicated. “Multiple” means two or more.

[0052] The terms "first" and "second" used in this document are for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined with "first" or "second" may explicitly or implicitly include one or more of that feature.

[0053] All figures in this application are approximate values, regardless of whether words such as "approximately" or "about" are used. The numerical values ​​may vary by 1%, 2%, 5%, 7%, 8%, 10%, etc. Whenever a figure with a value of N is disclosed, any figure with values ​​of N+ / -1%, N+ / -2%, N+ / -3%, N+ / -5%, N+ / -7%, N+ / -8%, or N+ / -10% will be explicitly disclosed, where "+ / -" indicates addition or subtraction, and the range from N-10% to N+10% is also disclosed.

[0054] Supramolecular cascade assembly enables cascaded energy transfer, resulting in multicolor and near-infrared luminescence, a current research hotspot with wide applications in information encryption, cell imaging, and catalysis. Utilizing cascade assembly through hydrogen-bonded host-guest interactions, π-π stacking, hydrophobicity, and electrostatic effects not only alters the topology of the assemblies, enhancing their luminescence performance, but also endows the system with dynamic reversibility and multiple stimulus responses. However, existing supramolecular cascade assemblies suffer from low energy transfer efficiency and difficulty in achieving full-spectrum tunable luminescence.

[0055] Unlike macrocyclic compounds that encapsulate guests, such as cyclodextrin, lithium saponite (LP) is a layered silicate nanomaterial with dual charge characteristics of positively charged edges and negatively charged surfaces. It is suitable as a host to assemble with various charged guest molecules to form high-performance supramolecular assemblies.

[0056] Lanthanide luminescent materials, due to their abundant energy level transitions, exhibit long excited states, large Stokes shifts, narrow emission bandwidths, high luminous efficiency, and good resistance to photobleaching, making them widely used in bioimaging, optical devices, information storage, sensors, and light-emitting diodes. Many lanthanide luminescent materials facilitate the cascade assembly of rare-earth ion coordination, enabling not only intelligent light-modulated multicolor emission but also near-infrared light emission, which is beneficial for the construction of intelligent biomaterials.

[0057] This invention proposes a tunable lanthanide supramolecular cascade full-color luminescent assembly material. By doping with near-infrared dyes such as Nile Red (NR: 600-750 nm), Nile Blue (NB: 600-800 nm), or Rhodamine 800 (Rh800: 650-850 nm), using vertically charged natural lithium saponite (LP) as the host scaffold and organic antenna molecules / lanthanide ion complexes as guest molecules, controllable modulation of long-lifetime near-infrared luminescence with an ultra-large Stokes shift (600 nm) is achieved. The use of LP not only restricts the non-radiative transition of organic antenna molecules through electrostatic interactions, thereby improving the energy transfer efficiency from organic antenna molecules to lanthanides and promoting lanthanide luminescence (18.7-fold increase in luminescence, 5.7-fold increase in quantum yield, and 6.9-fold increase in lifetime), but also provides an excellent platform for efficient supramolecular light-harvesting systems. After doping the assembly with dyes NR and NB, the effective energy transfer efficiencies from 545nm yellow-green light to 653nm and 665nm red light were 75% and 58%, respectively. Further doping with Rh800 resulted in energy transfer to the near-infrared region, peaking at 710nm, with a transfer efficiency exceeding 20%. This represents an unprecedented three-stage high-efficiency near-infrared light acquisition system based on rare-earth luminescence. Simultaneously, by combining pH changes with precise adjustment of the dye ratio, full-color control through time and ion editing can be achieved. This novel controllable, ultra-large Stokes shift rare-earth multi-level transfer full-color supramolecular component can be used as an anti-counterfeiting ink in the preparation of intelligent logic gate anti-counterfeiting materials, providing a new approach for the development of advanced anti-counterfeiting materials.

[0058] Specifically, the first aspect of the present invention provides a tunable lanthanide supramolecular cascade full-color luminescent assembly material, comprising:

[0059] The donor comprises a host and a guest, wherein the host is lithium saponite and the guest is an organic antenna molecule / lanthanide ion complex; the host and the guest form an assembly through host-guest interactions;

[0060] The receptor comprises a first dye and a second dye, wherein the first dye comprises either Nile Blue or Nile Red, and the second dye comprises Rh800.

[0061] "Organic antenna molecules" are a class of functional molecules that can efficiently absorb light of specific wavelengths and transfer energy to luminescent centers (such as rare earth ions).

[0062] In some embodiments, the organic antenna molecule comprises naphthalene-imidazolium pyridinecarboxylic acid (G1), which has the following structural formula: G1 exhibits highly efficient light-harvesting and energy-transfer capabilities. The pyridine dicarboxylic acid group in G1 is effective against lanthanide ions (such as Tb). 3+It has a high association constant, which allows G1 to form stable complexes with lanthanide ions.

[0063] In some embodiments, the lanthanide ions include Tb 3+ 、Tb 4+ Eu 3+ At least one of the following. These lanthanide ions have unique electronic structures, which enable them to exhibit excellent luminescent properties in luminescent materials.

[0064] In some embodiments, the mass ratio of the guest to the host is 0.001:(0.1-3). Optimizing the guest-to-host mass ratio is beneficial for enhancing the luminescence performance of lanthanide ions, increasing luminescence intensity and quantum yield, and extending emission lifetime. Too much or too little host addition is detrimental to improving the luminescence performance of lanthanide ions.

[0065] In some specific embodiments, the mass ratio of the object to the subject is 0.001:0.1, 0.001:0.2, 0.001:0.3, 0.001:0.4, 0.001:0.5, 0.001:1, 0.001:1.5, 0.001:2, 0.001:2.5, or 0.001:3. Preferably, the mass ratio of the object to the subject is 0.001:(0.1-1), and more preferably 0.001:0.3.

[0066] In some embodiments, the molar ratio of lanthanide ions to the first dye is 1:1 or higher, preferably 3:1-16:1, and more preferably 3:1. Optimizing the molar ratio of lanthanide ions to the first dye is beneficial to improving the energy transfer efficiency (Φ) from lanthanide ions to the first dye. ET This reduces energy waste and maximizes the energy conversion from donor to acceptor, thereby enhancing luminescence performance and improving material stability.

[0067] In some specific embodiments, the molar ratio of lanthanide ions to the first dye is 1:1, 2:1, 3:1, 4:1, 6:1, 8:1, 10:1, 12:1, 14:1, 16:1, 18:1, 20:1, 22:1, 25:1, 30:1, 33:1, 35:1, 40:1, 50:1, 60:1, 67:1, or 70:1.

[0068] In some embodiments, the molar ratio of the first dye to the second dye is 0.1:1 or higher, preferably 0.1:1 to 6:1, and more preferably 2:1. Optimizing the molar ratio of the first dye to the second dye is beneficial to improving the energy transfer efficiency from the first dye to the second dye, reducing energy waste, maximizing the energy conversion from donor to acceptor, thereby enhancing luminescent performance and improving material stability.

[0069] In some specific embodiments, the molar ratio of the first dye to the second dye is 0.1:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 4:1, 6:1 or 8:1.

[0070] In some embodiments, the molar ratio of lanthanide ions to the organic antenna molecules is 0.2:1-0.6:1, preferably 0.5:1. Optimizing the molar ratio of lanthanide ions to organic antenna molecules is beneficial for improving the fluorescence emission intensity of lanthanide ions.

[0071] In some specific embodiments, the molar ratio of lanthanide ions to the organic antenna molecules is 0.2:1, 0.3:1, 0.4:1, 0.5:1, or 0.6:1.

[0072] A second aspect of the present invention provides a method for preparing the tunable lanthanide supramolecular cascade full-color luminescent assembly material of the first aspect of the present invention, comprising the following steps:

[0073] Preparation of organic antenna molecule / lanthanide ion complexes;

[0074] The tunable lanthanide supramolecular cascade full-color luminescent assembly material can be obtained by co-assembling the organic antenna molecule / lanthanide ion complex, lithium saponite, the first dye, and the second dye.

[0075] The preparation method of this invention is simple, the conditions are mild, and it is highly reproducible, making it suitable for large-scale promotion.

[0076] In some embodiments, the preparation of the organic antenna molecule / lanthanide ion complex includes: mixing the organic antenna molecule with a salt containing lanthanide ions in water to obtain an organic antenna molecule / lanthanide ion complex solution.

[0077] In some embodiments, the salt containing lanthanide ions includes one or more of water-soluble nitrates, water-soluble sulfates, and water-soluble hydrochlorides.

[0078] In some specific embodiments, the salt containing lanthanide ions includes water-soluble nitrates.

[0079] In some embodiments, co-assembling the organic antenna molecule / lanthanide ion complex, lithium saponite, first dye, and second dye includes:

[0080] Lithium saponite was added to the organic antenna molecule / lanthanide ion complex solution, and the mixture was then used to obtain the donor solution.

[0081] A first dye is added to the donor solution, and after mixing, a second dye is added.

[0082] Upon addition of lithium saponite to the organic antenna molecule / lanthanide ion complex solution, the host and guest co-assemble through host-guest interactions to form a donor. This co-assembly can occur at room temperature.

[0083] The third aspect of this invention provides an application of the tunable lanthanide supramolecular cascade full-color luminescent assembly material of the first aspect of this invention in smart logic gate anti-counterfeiting materials.

[0084] The present invention will be explained below with reference to embodiments. Those skilled in the art will understand that the following embodiments are for illustrative purposes only and should not be considered as limiting the scope of the invention. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in the field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0085] Reagents and Materials: Unless otherwise stated, all chemicals were commercially available. NMR spectra were recorded on a Bruker AV500 spectrometer. Steady-state fluorescence data were acquired using a Varian Cary Eclipse fluorescence spectrometer and a Hitachi fluorescence spectrophotometer (F-4600S). UV-Vis spectra and transmittance were recorded using a quartz cell (optical path length, 10 mm) on a Shimadzu UV-3600 spectrophotometer equipped with a PTC-348WI temperature controller. Photoluminescence spectra and fluorescence lifetimes were measured by time-correlated single-photon counting on an FLS1000 instrument (edinburgh Instruments, Livingstone, UK). High-resolution transmission electron microscopy (TEM) images were obtained using a Tecnai 20 high-resolution TEM at an accelerating voltage of 200 keV. Zeta potentials were determined on a Nano-Bruker 90 Plus at 298 K.

[0086] Example 1: Synthesis of G1

[0087] Diethyl-4-(2-bromoethoxy)pyridine-2,6-dicarboxylic acid (CAS No.: 309254-57-7, structural formula: (690.04 mg, 2.0 mmol) and 1-(2-naphthylmethyl)-1H-imidazole (CAS No. 98318-77-5, structural formula is...) (416.2 mg, 2.0 mmol) was dissolved in 80 mL of CH3CN. The mixture was refluxed for about 24 h (monitored by TLC). After removing the solvent under vacuum, ethyl acetate was added and washed with H2O. The aqueous layer was dried under reduced pressure. A white solid was obtained, which dissolved in 20 mL of methanol. Then sodium hydroxide solution (160.5 mg, 4.0 mmol, 10 mL) was added. The resulting suspension was stirred at room temperature for 4 h. After removing the methanol under vacuum, the pH was adjusted to 4 using a 37% aqueous hydrogen chloride solution. The resulting precipitate was filtered, washed with water (3 × 30 mL), and dried under vacuum. The product was obtained as a white solid (736.4 mg, 74%). The 1H NMR spectrum of G1 is shown below. Figure 1 As shown.

[0088] Example 2: Construction of lithium saponite supramolecular assemblies (abbreviated as...) ) and G1 / Tb 3+ coordination compounds

[0089] LP was gradually added to an aqueous solution of G1 (G1 concentration was 0.02 mM) (the mass fraction of LP increased from 0.3 wt% to 3 wt%) (Note: In this invention, the mass fraction of LP refers to the proportion of the mass of LP to the mass of water), and after mixing, a lithium saponite supramolecular assembly was formed. Ultraviolet absorption gradually increases at 220nm and 250-300nm. Figure 2 a) until the mass fraction of LP reaches a maximum. The corresponding fluorescence spectrum shows that the emission at 335 nm continues to increase, and the fluorescence emission intensity increases by 22.6 times. Figure 2 (b) The fluorescence lifetime (from 17.50 ns to 24.40 ns) and quantum yield (from 0.13% to 3.79%) increased by 1.4-fold and 29.1-fold, respectively. This is likely due to the strong electrostatic interaction between the positive charge of G1 and the negative charge of the LP surface, which restricts the molecular rotation of G1, reduces nonradiative transitions, and promotes the blue fluorescence emission.

[0090] Simultaneously, the pyridine dicarboxylic acid group of G1 can form a lanthanide ion (Tb). 3+ Stable complexes with high association constants. Ultraviolet absorption spectrum ( Figure 2 c) shows that adding Tb to an aqueous solution of G1 (G1 concentration is 0.02 mM) 3+ Subsequently, the absorption at 270 nm gradually increases, the absorption peak at 220 nm gradually decreases, and an equal absorption point appears at 230 nm. A 490 nm peak is observed in the corresponding fluorescence spectrum. 5 D4→ 7 F6), 545nm 5 D4→7 F5), 583nm 5 D5→ 7 F4) and 621nm 5 D6→ 7 There are four sharp characteristic emission peaks at F3. Figure 2 d) with a lifetime of 0.14 ms and a yield of 0.45%, the transition from G1 to Tb was revealed. 3+ The energy transfer (ET) process. Based on ΔF (the change in complexation-induced fluorescence intensity at 545 nm) and Tb in the figure... 3+ The curve of / G1 molar ratio, Tb 3+ The stoichiometric ratio between G1 and G2 is 1:3. Figure 3 ).

[0091] Example 3: Based on LP and G1 / Tb 3+ supramolecular assemblies (abbreviated as) )

[0092] Gradually add LP to G1 / Tb 3+ The aqueous solution (G1 concentration is 0.02 mM, Tb) 3+ In a concentration of 0.0067 mM (where the mass fraction of LP increases from 0 wt% to 3 wt%), the absorption at 275 nm gradually increases, the absorption peak at 225 nm gradually decreases, and a uniform absorption point appears at 235 nm. Figure 4 a). Meanwhile, using pure water as the reference sample (Blank), the transmittance of G1 did not show any change, while the corresponding... The transmittance drops sharply at 400 nm, indicating that in G1 / Tb 3+ The addition of LP to the complex (G1 to Tb molar ratio of 3:1) leads to the formation of large nanostructure assemblies due to electrostatic interactions between the host and guest components. Figure 4 b) Complex G1 / Tb 3+ and assembly The Tyndall effect can clearly distinguish them. It is worth noting that when LP is added to the complex G1 / Tb... 3+ When the emission is moderate, it can be greatly enhanced by photoluminescence spectroscopy, and the best optical performance is achieved with an addition of 0.3 wt% LP. With the complex G1 / Tb 3+ In comparison, assemblies The luminous intensity increased by 18.7 times ( Figure 4 The quantum yield (c-4d) increased by 5.7 times, and the lifetime increased by 6.9 times. This phenomenon may be due to the electrostatic interaction restricting the nonradiative transitions of guest molecules, while the formation of assemblies also hinders the influence of H2O on rare earth coordination.

[0093] Furthermore, the assembly mode was further explored by altering the zeta potential and morphology of the assembly. This was achieved using transmission electron microscopy (TEM). Figure 5 )Observed G1, G1 / Tb 3+ Complex (G1 to Tb molar ratio 3:1) (Prepared from Example 2, LP mass fraction was 0.3 wt%) and The morphology of (prepared from Example 3, with a LP mass fraction of 0.3 wt%) changed from needle-like nanofibers and nanoparticles to many larger layered aggregates. Meanwhile, G1 / Tb 3+ The Zeta potential of the complex (G1 to Tb molar ratio of 3:1) increased from -15.70 mV for G1 to -2.36 mV, while The potential of (prepared from Example 3, with a mass fraction of LP of 0.3 wt%) from (Prepared from Example 2, with a mass fraction of LP of 0.3 wt%), the voltage increased from -35.52 mV to -29.17 mV. Figure 6 These data indicate that the coordination compound G1 / Tb 3+ The electrostatic interaction between the rare earth complex and the negatively charged LP surface forms a rare earth complex assembly.

[0094] Example 4: Based on Construction of cascaded energy transfer systems in supramolecular assemblies (abbreviated as) or )

[0095] Due to the assembly Exhibiting excellent rare-earth luminescence properties in aqueous phase (high quantum yield and long excitation lifetime), LPs possess an orthogonal multi-charge scaffold structure with negative surface charge and positive edge charge. This structure is suitable for selectively anchoring specific dyes to meet short-distance donor-acceptor requirements and achieving energy transfer from long-lifetime phosphors in the short-wavelength region to short-lifetime fluorophores in the near-infrared region, thus obtaining long-lifetime near-infrared fluorescence emission. In this study, we constructed a rare-earth luminescent supramolecular assembly based on LPs. This provides a suitable platform for efficient rare-earth light-harvesting energy transfer. Therefore, we selected water-soluble near-infrared luminescent dyes Nile Red (NR) and Nile Blue (NB), which possess high fluorescence quantum yields and are compatible with... Triple-state emission exhibits excellent spectral overlap, acting as an acceptor to ensure the feasibility of energy transfer. Figure 7 a and 7d). For example Figure 7 As shown in b and 7e, with the addition of NR or NB, (Prepared from Example 3, with LP mass fraction of 0.3 wt%), the emission peak at 490-600 nm gradually decreases, while the fluorescence peak at 600-800 nm in water gradually increases under 254 nm excitation. In time-resolved decay experiments, when the donor / acceptor (D / A) molar ratio is 3:1 (where D represents the donor), A represents the acceptor NR or NB, and the D / A molar ratio is equal to that of the lanthanide ion Tb. 3+ When the molar ratio with the first dye NR or NB is... Tb at 545 nm in aqueous solution 3+ The emission lifetimes decreased from 0.97 ms to 0.59 ms (NR) and 0.60 ms (NB), respectively. The fluorescence lifetime of NR at 653 nm was 18 μs, and that of NB at 665 nm was 19 μs, significantly longer than those of NR (1.70 ns) and NB (0.74 ns). Correspondingly, the quantum yields in the 490–600 nm range decreased from 2.31% to 0.48% (NR) and 0.56% (NB), respectively, while the quantum yields in the 600–800 nm range increased from 0.38% to 6.52% and 4.92%, respectively. These results indicate that resonant energy transfer in rare-earth luminescence occurs from the donor... The triplet state is converted to the singlet state of the acceptor NR or NB. Furthermore, the energy transfer efficiency ФET quantifies the change in donor emission intensity in the presence of different acceptor concentrations and is an important indicator for quantitatively evaluating the efficiency of a light-harvesting system. Based on the shortened lifetime data of the acceptor, the ФET values ​​for a D / A molar ratio of 3:1 were determined to be 75% (NR) and 58% (NB), respectively. Figure 7 c and 7f). Meanwhile, under the same experimental conditions, with or without assemblies... In the case of NR and NB, the spectra show negligible fluorescence emission, while and Significant delayed fluorescence emission can be observed, indicating the existence of efficient rare-earth luminescent energy transfer from donor to acceptor.

[0096] Example 5: Based on Construction of efficient cascaded energy transfer systems for supramolecular assemblies (abbreviated as...) or To achieve longer-wavelength, long-life near-infrared emission, we used... and (All were prepared in Example 4, with a D / A molar ratio of 3:1) as the energy donor, a rare-earth luminescent cascade energy transfer was studied using Rhodamine 800 (Rh800) dye emitting in the near-infrared region as the energy acceptor. Its absorption and... or The emission has good spectral overlap ( Figure 8 a and Figure 8 d). In As Rh800 was gradually added to the solution, the fluorescence intensity at 653 nm gradually decreased. Figure 8 (b) The lifetime and quantum yield decreased to 17 μs and 3.40%, respectively, while the fluorescence intensity at 710 nm gradually increased. The lifetime of the monomeric Rh800 increased from 0.12 ns to 8.50 ms, and the quantum yield increased by 1.4 times (from 2.22% to 3.08%). This was based on the energy transfer process... Fluorescence quenching occurs when the D / A molar ratio is 1:1 (for assemblies). and D represents the donor. When A represents the acceptor Rh800, and the D / A molar ratio is equal to the molar ratio of the first dye NR or NB to the second dye Rh800, the energy transfer efficiency is 27%. Figure 8 c). Similarly, as Rh800 is gradually added... After being placed in solution, the fluorescence intensity, fluorescence lifetime, and quantum yield at 665 nm decreased (to 18 ms and 2.15%, respectively). Figure 8 e) The fluorescence intensity, fluorescence lifetime, and quantum yield at 710 nm gradually increased (lifetime increased from 0.12 ns for Rh800 to 14 ms, and quantum yield increased from 2.19% to 2.79%). When the D / A molar ratio was 2:1, the energy transfer efficiency was 21%. Figure 8 f). Meanwhile, in the control experiment, we also selected two different dyes, Rhodamine B (RhB) and silicon-based Rhodamine (SIR), and found that as the dyes were gradually added... (Prepared from Example 3, with LP having a mass fraction of 0.3 wt%), The fluorescence at 545 nm did not change significantly. Figure 9 ab and Figure 9 (de). In the absence of NR and NB, when When Rh800 is used directly as a fluorescence donor and as a fluorescence acceptor, the emission peak at 545 nm remains almost unchanged. Figure 9 c and 9f). These results collectively validate the interaction between fluorescent dyes NR or NB and Rh800 and multicharge. Aggregates form co-assemblies and can achieve cascaded energy transfer. To our knowledge, such efficient cascaded energy transfer based on rare-earth luminescence, especially the large Stokes shift of nearly 600 nm from 254 nm to 850 nm, is rarely reported. Furthermore, given the excellent rare-earth luminescence energy transfer properties across the large Stokes shift of 600 nm from the ultraviolet to the near-infrared region, we can achieve this by simply adjusting the ligands G1 and Tb in the multivalent supramolecular assemblies. 3+ And the D / A ratio is used to quickly adjust the emitted color, thereby achieving a wide-spectrum output of full-color photoluminescence. For example... Figure 8 As shown in g-8h, with ligand / Tb 3+ With the change in proportion, the luminescence color of the supramolecular assembly aqueous solution changed from blue to green. Subsequently, primary energy transfer dye NR and secondary energy transfer dye Rh800 were successively added to the assembly. In the middle. With the D / A molar ratio (D is... or A is a change in Rh800, and the luminescence color of the assembled aqueous solution changes from green to red. In the CIE (International Commission on Illumination) xy chromaticity diagram, pure Complexes and The coordinates at a D / A ratio of 0.5:1 correspond to (0.16, 0.06), (0.32, 0.52), and (0.54, 0.39), respectively. NR is in the blue emitting component. The gradual addition of elements can also adjust the emission from blue to red, corresponding to CIE coordinates of (0.16, 0.06) to (0.54, 0.21). Then, based on the blue emission assembly... Green light emitting Tb 3+ By adjusting the ratio of the orange-red emitting NR and the red emitting Rh800, a full-color spectrum output can be achieved. Interestingly, in In the CIE diagram, when the D / A molar ratio is 1:1, white light with chromatic coordinates (0.31, 0.33) is obtained, which is very close to the accurate white light point (0.33, 0.33). Figure 8 i). exist Figure 8 j explains Possible mechanisms of rare-earth luminescent cascade transfer during assembly. Guest G1 and Tb 3+ After complexation, the 2,6-pyridinedicarboxylic acid moiety of G1 can act as a sensitizer or antenna to absorb excitation light with a high absorption coefficient. Then, energy is transferred to lanthanide ions through intersystem crossover, resulting in Tb 3+ In the excited state. The negatively charged surface of LP is in contact with G1 / Tb. 3+Electrostatic interactions between the naphthalimazole salts of the complex restrict the nonradiative transition of the antenna molecule G1. The orthogonal charge accumulation of LPs can, to some extent, protect the Tb centers from collisions with oxygen in water, promoting Tb luminescence. On the other hand, the remaining negatively charged surface of LPs provides a platform for energy transfer, allowing for continuous assembly with cationic dyes, thereby shortening the distance between the donor and acceptor and achieving efficient, long-lived rare-earth luminescent cascade energy transfer in the aqueous phase.

[0097] Example 6: LP supramolecular components are suitable for multi-level information encryption

[0098] The adjustable full-color light-emitting component of this invention can be applied to multi-level logic gate anti-counterfeiting and information encryption. As shown in Figure (10a), different components of the assembly define the input, and the white light emission excited by 254nm is defined as the output. Based on the white light output recorded as "1" and the non-white light output recorded as "0", we designed a continuous logic gate system for suppressing white light output. It is worth noting that the current output "0" and "1" states of the logic gate represent several different types of supramolecular assemblies. In the logic gate system, when (Prepared from Example 4, D / A molar ratio of 3:1) When coexisting, white light emission can be "locked," and the Rh800 is used as the "mute" output signal of the NOT gate, which is clearly shown in the truth table. Figure 11 A continuous logic gate system defines the binary code of the design as the output. When (Prepared from Example 5, D / A molar ratio of 2:1) and H + When coexisting, the designed binary code can be "locked". Then, the binary code of the above output design is converted to hexadecimal, the hexadecimal codes of different assemblies are translated into Unicode, and finally the classical Chinese poems are output. Based on the logic gate of this LP rare earth multi-color cascaded energy transfer component, we prepared a multi-level data encryption system with a four-color microarray according to the standard 16-bit ASCII binary and hexadecimal codes. Among them, black dots represent "00"; green fluorescent dots represent "01"; white fluorescent dots represent "10"; and red fluorescent dots represent "11". Initially, the complex G1 / Tb solution (G1 concentration is 0.02mM, Tb concentration is 0.02mM) in the multi-well plate. 3+ The pattern dots in each row of the sample (at a concentration of 0.0067 mM) barely emitted light under 254 nm UV light, used to collect the binary code "000000000000". These binary codes are meaningless when converted to characters and hexadecimal according to ASCII encoding rules. Interestingly, after adding LP to some G1 / Tb holes, green fluorescence clearly emitted at 254 nm, which, combined with ASCII encoding rule information, could be deciphered into specific characters and hexadecimal codes. Figure 12-13More importantly, we can select specific, important information for translation at each step of the encryption process. For example, in the second step, the specified encrypted information can be decrypted into the character "DATE". In the third step, NR is added to a specific green orifice to form a white luminescent component; excess NR forms a red luminescent component, used to decipher the character "NKU" at the specified location in the encrypted information. In the fourth step, dye Rh800 is added to a specific area, and the specified encrypted information is selected to obtain the character "immu". The next step can be to... + or OH - Added to specific areas to adjust selected encryption information for the character "lOVe". Furthermore, we successfully applied the component to multi-level digital encryption. For example... Figure 10 As shown in b, the G1 solution (0.02 mM) was filled into the multi-well plate in the form of the number "2825", where the numbers "1975" and "2025" were encrypted and almost invisible under 254 nm irradiation. Tb was added to the multi-well plate. 3+ Afterward, it becomes almost invisible. Adding the host molecule LP results in a blue and green emission number "1111". Adding the receptor NR results in emission numbers "1771" in different colors (blue, green, white, and yellow, respectively). When the second receptor Rh800 is added, the first encrypted emission number "1975" appears in different colors (green, white, and orange-red, respectively). Based on this, by adding H... + or OH - This allows deciphering the second, different-colored encrypted glowing number, "2025". By calculating the R / G value, in... The addition of first-order energy transfer dye NR and second-order energy transfer dye Rh800 yielded good linearity. Figure 10 c).

[0099] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0100] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A tunable lanthanide supramolecular cascade full-color luminescent assembly material, characterized in that, include: The donor comprises a host and a guest, wherein the host is lithium saponite and the guest is an organic antenna molecule / lanthanide ion complex; the host and the guest form an assembly through host-guest interactions; The receptor comprises a first dye and a second dye, wherein the first dye comprises either Nile Blue or Nile Red, and the second dye comprises Rh800.

2. The tunable lanthanide supramolecular cascade full-color luminescent assembly material according to claim 1, characterized in that, The organic antenna molecule includes G1, which has the following structural formula:

3. The tunable lanthanide supramolecular cascade full-color luminescent assembly material according to claim 1, characterized in that, The lanthanide ions include Tb 3+ 、Tb 4+ Eu 3+ At least one of them.

4. The tunable lanthanide supramolecular cascade full-color luminescent assembly material according to claim 1, characterized in that, The mass ratio of the object to the subject is 0.001:(0.1-3), preferably 0.001:(0.1-1).

5. The tunable lanthanide supramolecular cascade full-color luminescent assembly material according to claim 1, characterized in that, The molar ratio of lanthanide ions to the first dye is 1:1 or higher, preferably 3:1 to 16:1; The molar ratio of the first dye to the second dye is 0.1:1 or higher, preferably 0.1:1 to 6:

1.

6. The tunable lanthanide supramolecular cascade full-color luminescent assembly material according to claim 1, characterized in that, The molar ratio of lanthanide ions to the organic antenna molecules is 0.2:1 to 0.6:

1.

7. A method for preparing the tunable lanthanide supramolecular cascade full-color luminescent assembly material according to any one of claims 1-6, characterized in that, Includes the following steps: Preparation of organic antenna molecule / lanthanide ion complexes; The tunable lanthanide supramolecular cascade full-color luminescent assembly material can be obtained by co-assembling the organic antenna molecule / lanthanide ion complex, lithium saponite, the first dye, and the second dye.

8. The method according to claim 7, characterized in that, The preparation of organic antenna molecule / lanthanide ion complex includes: mixing the organic antenna molecule with a salt containing lanthanide ions in water to obtain an organic antenna molecule / lanthanide ion complex solution; The salts containing lanthanide ions include one or more of water-soluble nitrates, water-soluble sulfates, and water-soluble hydrochlorides.

9. The method according to claim 8, characterized in that, The co-assembly of the organic antenna molecule / lanthanide ion complex, lithium saponite, first dye, and second dye comprises: Lithium saponite was added to the organic antenna molecule / lanthanide ion complex solution, and the mixture was then used to obtain the donor solution. A first dye is added to the donor solution, and after mixing, a second dye is added.

10. The application of the tunable lanthanide supramolecular cascade full-color luminescent assembly material according to any one of claims 1-6 in smart logic gate anti-counterfeiting materials.

Images