A eutectic material with ion-stimulated fluorescence response and its preparation method
By forming eutectic materials with cyclophosphamide and crown ethers, and utilizing host-guest interactions and intermolecular interactions, the problem of fluorescent materials with ion-stimulated responses in the solid state was solved, achieving high spatiotemporal resolution and high sensitivity fluorescence response, thus expanding applications in information security and optical anti-counterfeiting.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- ANHUI UNIV
- Filing Date
- 2023-11-07
- Publication Date
- 2026-05-26
AI Technical Summary
Existing technologies struggle to achieve fluorescent materials with ion-stimulated responses in the solid state, especially the dynamic properties and fluorescence response of eutectic composites, and their applications in information security and sensing are limited.
Co-crystal materials are formed through the host-guest interaction between cyclophenes and crown ethers. Co-crystal materials with ion-stimulated fluorescence response characteristics are prepared by utilizing the interactions such as CH-Π, Π-Π and hydrogen bonds.
The fluorescence response characteristics of eutectic materials under external ion stimulation were realized, exhibiting high spatiotemporal resolution and high sensitivity, making them suitable for fields such as information security and optical anti-counterfeiting.
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Figure CN117551099B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of fluorescent materials technology, and particularly relates to a eutectic material with ion-stimulated fluorescence response characteristics and its preparation method. Background Technology
[0002] Stimulus-responsive materials are a class of molecules with "intelligent" behavior, capable of generating corresponding response signals in response to external environments (such as light, temperature, pressure, humidity, etc.), such as changes in color, electronic properties, mechanical properties, and other physicochemical properties. These materials can then be used in sensors, detectors, and probes, showing broad application prospects in information technology, biosensing, and medical testing. Among these, organic fluorescent eutectic materials with ion-stimulus-responsive functions are particularly noteworthy, with significant scientific and application backgrounds. The structure of these materials can be altered by introducing different ions, resulting in changes in fluorescence and thus exhibiting superior performance in information security, response, and sensing. Currently, while purely organic fluorescent materials with stimulus-responsive properties are a research hotspot in the field of organic light-emitting materials, they also represent a significant challenge.
[0003] Over the past few decades, significant efforts have been made in constructing variable supramolecular topological complexes. While the ultimate goal of supramolecular complexes is to achieve control over intrinsic stimulus responsiveness based on the cavity of the ring, realizing the dynamic properties of topological structures in the solid state remains a challenge. Therefore, utilizing the tunability of supramolecular topologies to achieve fluorescence responses to ion stimulation has been an important research direction for achieving solid-state responses. Some sporadic reports have explored the use of guest recognition techniques to construct advanced ternary complexes through interactions between inner-ring guests and ions / small organic molecules, or the realization of dynamic complexes in solution, such as the complexation of cyclic terephthalic acid with metallofullerenes or chiral ring-in-ring complexes. However, reports on using eutectic complex materials to achieve effective solid-state responses to ion stimulation are very limited. Summary of the Invention
[0004] Based on the above-mentioned technical problems, the present invention provides a eutectic material with ion-stimulated fluorescence response characteristics and its preparation method. The eutectic material is obtained by using a fluorescent cyclophenone as the host and a crown ether as the guest, and the two are combined by host-guest interaction. It not only has the characteristics of ion-stimulated fluorescence response, but also has the advantages of high spatiotemporal resolution and good sensitivity.
[0005] The present invention proposes a co-crystal material with ion-stimulated fluorescence response characteristics, which is a co-crystal compound formed by the interaction of fluorescent cyclophenes and crown ethers through host-guest interactions.
[0006] Preferably, the subject-guest function is that the crown ether, as a guest, penetrates into the inner pore of the cyclic ether, which is the subject.
[0007] Preferably, the cyclic algebra is a cyclic algebra represented by the following structural formula I:
[0008]
[0009] Preferably, the crown ether is a crown ether represented by the following structural formulas II, III, and IV:
[0010]
[0011]
[0012] Preferably, the ion is a metal ion, and more preferably a potassium ion.
[0013] This invention proposes a method for preparing a eutectic material with ion-stimulated fluorescence response characteristics, comprising: mixing the cyclophosphamide with a crown ether, adding an organic solvent for grinding to obtain a powdered composite; dissolving the powdered composite in an organic solvent, and evaporating the organic solvent at room temperature or low temperature to obtain a single-crystal compound, which is the eutectic material.
[0014] Preferably, the molar ratio of the cyclophosphamide to the crown ether is 1:1-3.
[0015] Preferably, the organic solvent is at least one of acetone, acetonitrile, dichloromethane, or methanol.
[0016] Preferably, the grinding time is 20-60 minutes.
[0017] The present invention also proposes the application of the above-mentioned eutectic material or the eutectic material prepared by the above-mentioned preparation method in optical anti-counterfeiting or encryption.
[0018] This invention uses cyclophenones with fluorescent effects as the host and traditional crown ethers as the guest. Cyclophenones and crown ethers undergo intermolecular interactions (CH-Π, Π-Π, hydrogen bonding interactions) at the microscale with specific stoichiometric ratios to generate solid eutectic compounds. This achieves modulation of the molecular solid packing form and spatial arrangement structure, resulting in a novel binary eutectic material with ion-stimulated fluorescence response characteristics.
[0019] The eutectic material described in this invention utilizes the strong CH-Π and hydrogen bond interactions between the cyclophosphide and the crown ether, giving the eutectic material novel fluorescence properties. It exhibits different fluorescence response modes and response speeds under external stimuli (the addition of ionic solutions). This unique property can be further applied to time-gated information security and encryption, and has broad application prospects in fields such as information encryption, fluorescence sensors, and optical devices.
[0020] This invention reveals the relationship between the topological structure of cyclophosphide-based eutectic compounds and the strength of intermolecular interactions, as well as the influence of metal ions on the fluorescence properties of crown ether-containing eutectic compounds. This expands the scope of preparation and application of host-guest eutectic materials, and brings significant insights and innovations, especially for the preparation of fluorescent materials and optical anti-counterfeiting devices in the field of information security. Attached Figure Description
[0021] Figure 1 The above are the 1H NMR spectra of the tetracationic cyclopane, dibenzo-24-crown-8 and eutectic materials described in Example 1.
[0022] Figure 2 The above are the 1H NMR spectra of the tetracationic cyclopane, bis(m-phenyl-32-crown-10), and eutectic material described in Example 2.
[0023] Figure 3 The above are the 1H NMR spectra of the tetracationic cyclopane, bis-1,5-dinaphth-50-crown-14 and the eutectic material described in Example 3.
[0024] Figure 4 The single-crystal X-ray diffraction pattern of the eutectic material described in Example 1;
[0025] Figure 5 The single-crystal X-ray diffraction pattern of the eutectic material described in Example 2;
[0026] Figure 6 The single-crystal X-ray diffraction pattern of the eutectic material described in Example 3;
[0027] Figure 7 The solid ultraviolet absorption spectra of the eutectic materials described in Examples 1-3 are shown below.
[0028] Figure 8 The fluorescence spectra of the eutectic materials described in Examples 1-3 are shown below.
[0029] Figure 9 Fluorescence spectra of the eutectic material described in Example 1 before and after the addition of an acetonitrile / isopropyl ether (1 / 9) solution containing potassium ions;
[0030] Figure 10 The fluorescence spectra of the eutectic material described in Example 2 before and after the addition of an acetonitrile / isopropyl ether (1 / 9) solution containing potassium ions;
[0031] Figure 11 The fluorescence spectra of the eutectic material described in Example 3 before and after the addition of a potassium-containing acetonitrile / isopropyl ether (1 / 9) solution are shown. Detailed Implementation
[0032] The present invention will now be described in detail through specific embodiments. However, these embodiments are clearly provided for illustrative purposes and are not intended to limit the scope of the present invention.
[0033] Example 1
[0034] This embodiment presents a eutectic material with ion-stimulated fluorescence response characteristics, which is prepared by the following method:
[0035] (1) Weigh 0.010g of tetracationic cyclopane (represented by Box) as shown in structural formula I and 0.0057g of dibenzo-24-crown-8 (represented by DB24C8) as shown in structural formula II respectively;
[0036] (2) Mix the above-mentioned tetracationic cyclopane and dibenzo-24-crown-8 evenly and add them to a mortar. Then add 50 μL of acetonitrile and grind thoroughly at room temperature for 40 min to obtain a powdered complex.
[0037] (3) Dissolve the above-mentioned powdered composite in 5 mL of acetonitrile, and allow the solvent to evaporate at room temperature to obtain the eutectic material (as shown in the figure). express).
[0038] Example 2
[0039] This embodiment presents a eutectic material with ion-stimulated fluorescence response characteristics, which is prepared by the following method:
[0040] (1) Weigh 0.010g of tetracationic cyclopane (represented by Box) as shown in structural formula I and 0.0093g of bis(m-phenyl-32-crown-10) (represented by BMP32C10) as shown in structural formula III respectively;
[0041] (2) Mix the above tetracationic cyclophenanthrene and bis(m-phenyl-32-crown-10) evenly and add them to a mortar. Then add 40 μL of acetonitrile and grind thoroughly at room temperature for 40 min to obtain a powdered complex.
[0042] (3) The powdered composite was dissolved in 10 mL of acetonitrile, and the solvent was allowed to evaporate at room temperature to obtain the eutectic material. express.
[0043] Example 3
[0044] This embodiment presents a eutectic material with ion-stimulated fluorescence response characteristics, which is prepared by the following method:
[0045] (1) Weigh out 0.010g of tetracationic cyclopane (represented by Box) as shown in structural formula I and 0.0093g of bis-1,5-dinaphthyl-50-crown-14 (represented by DNP50C14) as shown in structural formula IV respectively;
[0046] (2) Mix the above tetracationic cyclophenanthrene and bis(m-phenyl-32-crown-10) evenly and add them to a mortar. Then add 50 μL of acetonitrile and grind thoroughly at room temperature for 40 min to obtain a powdered complex.
[0047] (3) The powdered composite was dissolved in 10 mL of acetonitrile, and the solvent was allowed to evaporate at room temperature to obtain the eutectic material. express.
[0048] Figure 1 The image shows the 1H NMR spectrum of the tetracationic cyclopane, dibenzo-24-crown-8, and eutectic material described in Example 1. (Refer to...) Figure 1 It is known that the eutectic material obtained by the interaction between the host and guest tetracation cyclophenones and dibenzo-24-crown-8 through CH-Π, Π-Π, hydrogen bonds, etc., has a certain change in the chemical shift of hydrogen on the aromatic ring (slightly shifted to the left) relative to the tetracation cyclophenones and dibenzo-24-crown-8. This change is caused by the Π electron shielding of the face-to-face aromatic rings.
[0049] After performing single-crystal X-ray diffraction characterization on the eutectic material described in Example 1, Figure 4 This is a single-crystal X-ray diffraction pattern of the eutectic material described in Example 1. (Refer to...) Figure 4 It is known that dibenzo-24-crown-8 penetrates into the tetracation cyclopane cavity and is encapsulated within it, forming a 1:1 host-guest complex. This complex is stabilized through CH-Π, Π-Π, and hydrogen bond interactions. In other words, the tetracation cyclopane and dibenzo-24-crown-8 form a new crystal structure, which can be used to explain why the resulting eutectic material has different fluorescence properties.
[0050] Figure 2 The image shows the 1H NMR spectrum of the tetracationic cyclopane, bis(m-phenylene-32-crown-10), and eutectic material described in Example 2. (Refer to...) Figure 2 It is known that the eutectic material obtained by the interaction between the tetracationic cyclophenene and bis-phenyl-32-crown-10 via CH-Π, Π-Π, hydrogen bonds, etc., between the host and guest exhibits a certain change in the chemical shift of hydrogen on the aromatic ring relative to the tetracationic cyclophenene and bis-phenyl-32-crown-10 (a slight rightward shift). This change is caused by the Π electron shielding of the face-to-face aromatic rings.
[0051] After performing single-crystal X-ray diffraction characterization on the eutectic material described in Example 2, Figure 5This is a single-crystal X-ray diffraction pattern of the eutectic material described in Example 2. (Refer to...) Figure 5 It is known that the bis-m-phenyl-32-crown-10 molecules are arranged head-to-tail and penetrate the cavity of the tetracationic cyclopane to form a host-guest complex. The tetracationic cyclopane and bis-m-phenyl-32-crown-10 also recombine to form a new crystal structure, which can be used as an explanation for the different fluorescent properties of the obtained eutectic material.
[0052] Figure 3 The above is the 1H NMR spectrum of the tetracationic cyclopane, bis-1,5-dinaphth-50-crown-14, and the eutectic material described in Example 3. (Refer to...) Figure 3 It is known that the eutectic material obtained by the interaction between the host and guest groups of tetracationic cyclophenene and bis-1,5-dinaphthyl-50-crown-14 via CH-Π, Π-Π, hydrogen bonds, etc., shows a significant change in the chemical shift of hydrogen relative to tetracationic cyclophenene and bis-1,5-dinaphthyl-50-crown-14 (a large shift to the right). This change is caused by the Π electron shielding of the face-to-face aromatic rings.
[0053] After performing single-crystal X-ray diffraction characterization on the eutectic material described in Example 3, Figure 6 This is a single-crystal X-ray diffraction pattern of the eutectic material described in Example 3. (Refer to...) Figure 6 It is known that bis-1,5-dinaphthyl-50-crown-14 also penetrates into the rigid tetracationic cyclopane and is forced to twist into a "Z"-shaped structure. The tetracationic cyclopane and bis-1,5-dinaphthyl-50-crown-14 also recombine to form a new crystal structure, which can be used as an explanation for the different fluorescent properties of the obtained eutectic material.
[0054] Figure 7 The images show the solid-state ultraviolet absorption spectra of the eutectic materials described in Examples 1-3. (Refer to...) Figure 7 It can be seen that the eutectic materials described in Examples 1, 2 and 3 exhibit gradually deepening yellow, orange and red colors, which is consistent with the phenomenon of the charge transfer absorption band gradually red-shifting observed in the solid-state ultraviolet absorption spectrum of crystals, indicating that the degree of charge transfer gradually increases in the three eutectic materials.
[0055] Figure 8 The fluorescence spectra of the eutectic materials described in Examples 1-3 are shown. (Refer to...) Figure 8 It can be seen that the solid absorption peak of the eutectic materials described in Examples 1 and 3 lasts up to 660 nm without fluorescence emission. This indicates that dibenzo-24-crown-8 and bis-1,5-dinaphthyl-50-crown-14, as guest atoms, quenched the fluorescence of tetracationic cyclophene as the host. The eutectic material described in Example 2 changed from emitting blue light (fluorescence emission shift of tetracationic cyclophene at 430 nm) to emitting yellow light (557 nm). This indicates that bis-m-phenyl-32-crown-10, as a guest atom, altered the fluorescence of tetracationic cyclophene as the host.
[0056] Figure 9 Fluorescence spectra of the eutectic material described in Example 1 before and after the addition of an acetonitrile / isopropyl ether (1 / 9) solution containing potassium ions. (Refer to...) Figure 9 It can be seen that the fluorescence spectrum of the eutectic material described in Example 1 changes from zero to present before and after the addition of a solution containing potassium ions. This is because potassium ions can bind to the crown ether molecules in the eutectic material, thereby enabling the fluorescence of the eutectic material to be activated.
[0057] Figure 10 Fluorescence spectra of the eutectic material described in Example 2 before and after the addition of an acetonitrile / isopropyl ether (1 / 9) solution containing potassium ions. (Refer to...) Figure 10 It can be seen that the fluorescence spectrum of the eutectic material described in Example 2 changed to blue shift before and after the addition of a solution containing potassium ions. This is because potassium ions can bind to crown ether molecules in the eutectic material, thereby changing the fluorescence of the eutectic material.
[0058] Figure 11 Fluorescence spectra of the eutectic material described in Example 3 before and after the addition of a potassium-containing acetonitrile / isopropyl ether (1 / 9) solution. (Refer to...) Figure 11 It can be seen that the fluorescence spectrum of the eutectic material described in Example 2 changes from zero to present before and after the addition of a solution containing potassium ions. This is because potassium ions can bind to the crown ether molecules in the eutectic material, thereby enabling the fluorescence of the eutectic material to be activated.
[0059] As shown above, changing the ring size of a series of crown ether compounds alters the binding mode with the tetracation cyclophene. Due to the varying magnitudes of intermolecular forces in different eutectic materials, the fluorescence properties of the eutectic materials also differ. Based on this, the excellent binding ability of crown ethers to alkali metal ions is utilized to disrupt the binding between the tetracation cyclophene and the crown ether molecules, eliminating the intermolecular forces that affect luminescence and thus enabling the activation or alteration of fluorescence. Furthermore, considering the varying binding abilities between different crown ethers and alkali metal ions, the binding ability gradually decreases as the crown ether size increases. Therefore, different eutectic materials will exhibit fluorescence responses to ion stimulation at different time gradients, demonstrating different time-dependent characteristics.
[0060] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.
Claims
1. A co-crystal material having an ion-stimulated fluorescent response characteristic, characterized in that, It is a co-crystallized compound formed by a fluorescent cyclophenone and a crown ether through a host-guest interaction; The subject-object function is that the crown ether, as the object, penetrates into the inner pore of the cyclic ether, which is the subject; The cyclic algebra is a cyclic algebra represented by the following structural formula I: The crown ether is a crown ether shown in the following structural formulae II, III, and IV: , , The co-crystal material is prepared by the following method: mixing cyclophane and crown ether, adding organic solvent for grinding to obtain a powdery compound; the powdery compound is dissolved in an organic solvent again, and the organic solvent is volatilized at room temperature to obtain a single crystal compound, that is, the co-crystal material. The molar ratio of the cyclophosphamide to the crown ether is 1:1-3; the organic solvent is acetonitrile.
2. A method for producing a co-crystal material having an ion-stimulated fluorescent response characteristic, characterized by, The eutectic material is a co-crystallized compound formed by a fluorescent cyclophenone and a crown ether through a host-guest interaction; The subject-object function is that the crown ether, as the object, penetrates into the inner pore of the cyclic ether, which is the subject; The cyclic algebra is a cyclic algebra represented by the following structural formula I: The crown ether is a crown ether shown in structural formula II, III or IV: 、 、 The preparation method comprises the following steps: mixing the cyclodextrin and the crown ether, adding an organic solvent for grinding to obtain a powdery compound; the powdery compound is dissolved in an organic solvent again, and the organic solvent is volatilized at room temperature to obtain a single crystal compound, that is, the eutectic material. The molar ratio of the cyclophosphamide to the crown ether is 1:1-3; the organic solvent is acetonitrile.
3. The method for preparing the eutectic material with ion-stimulated fluorescence response characteristics according to claim 2, characterized in that, The grinding time is 20-60 minutes.
4. The application of the eutectic material of claim 1 in ion-stimulated fluorescent response materials.
5. The application of the eutectic material according to claim 4 in ion-stimulated fluorescence-responsive materials, characterized in that, The stimulating ion used is potassium ion.