Spiroaromatic hydrocarbon-based micro-nano crystal polyhedron assembly, morphology regulation and control and assembly method

Abstract

The invention discloses a spirocyclic aromatic hydrocarbon-based micro-nano crystal polyhedron assembly method, a spirocyclic aromatic hydrocarbon-based morphology control method and a spirocyclic aromatic hydrocarbon-based micro-nano crystal polyhedron assembly method, and relates to the technical field of organic nano materials. The molecular configuration of the spirocyclic aromatic hydrocarbon molecule is that two crossed planes share one central carbon atom, and the shape of the micro-nano crystal is a three-dimensional polyhedron. According to the spiroaromatic hydrocarbon-based micro-nano crystal polyhedron assembly, morphology regulation and control and assembly method, SAHs are not connected with any substituent group, the self-assembly morphology of SAHs is a polyhedron structure, the fluorene surface of SAHs is endowed with different SSH effects by performing tiny structural adjustment on the fluorene surface on the basis of not changing the molecular configuration, and crystal morphology regularity regulation and control are further induced.

Description

Technical Field

[0001] The invention relates to the technical field of organic nanomaterials, and in particular to a micro-nano crystal polyhedron assembly, morphology control and assembly method based on spiroaromatic hydrocarbons. Background Art

[0002] Functional organic micro / nanomaterials, as an important and urgently needed component in the field of chemical engineering, have received increasing attention in future-oriented optoelectronic devices. Although great progress has been made in organic micro / nanomaterials in charge transport, high-density charge storage, nonlinear optics, delayed fluorescence, and biological applications, the self-assembly process still faces challenges. Unlike inorganic systems, organic molecules have condensed molecular configurations and conformations, which have an important influence on supramolecular interactions, which in turn determine the molecular stacking pattern and final crystal morphology. The role of different functional groups in organic systems and the complex interplay of multiple intermolecular interactions remain unclear, making it difficult to obtain accurate morphological predictions.

[0003] The spatial supramolecular steric hindrance (SSH) effect, which originates from the combination of steric hindrance groups and supramolecular fragments, regulates and controls the stacking of molecules through supramolecular interactions and further finely tunes the exciton behavior, thereby improving the quantum yield and spectral stability. The rational design of supramolecular macromolecules is a promising approach to overcome intrachain repulsion and flatten the main chain, leading to β-phase polyfluorene films with good spectral stability and also demonstrating the mechanism of green band emission. In addition, the introduction of supramolecular heteroatoms in the molecular system provides a method to precisely regulate the π stacking of intermolecular interactions and leads to the formation of excimers, which can further explain the defect emission by establishing new molecular models. It is also proved that the SSH effect is a powerful tool for the rational design and assembly of various micro / nanostructures. The strategy of integrating supramolecular fragments and macromolecular groups into one molecule has been shown to be an effective method for the two-dimensional assembly of nanosheets. In addition, various highly symmetrical polyhedra have been obtained by the self-assembly of reprecipitated macromolecules. However, the role of the SSH effect in the self-assembly of symmetrical polyhedra is still unclear.

[0004] The spatial supramolecular steric hindrance (SSH) effect originates from the combination of steric hindrance groups and supramolecular fragments. The molecular stacking is regulated by the interaction between supramolecular molecules, and the behavior of excitons is further finely regulated, which improves the quantum yield and spectral stability. The rational design of supramolecular steric hindrance molecules is a promising method to overcome intrachain repulsion and planarize the main chain. β-phase polyfluorene films with good spectral stability are achieved, and the mechanism of green band emission is also demonstrated. In addition, the introduction of supramolecular heteroatoms into the molecular system provides a method for precisely regulating the interaction between molecules. By establishing a new molecular model, the defect emission is further explained, and the SSH effect is proved to be a powerful tool for the rational design and assembly of various micro-nanostructures. The strategy of integrating supramolecular segments and steric hindrance groups into one molecule has been shown to be an effective method for the assembly of two-dimensional nanosheets. In addition, the self-assembly of steric hindrance molecules can obtain various highly symmetrical polyhedra by reprecipitation. However, the role of the SSH effect in the self-assembly of symmetrical polyhedra is still unclear.

[0005] Therefore, in view of this, the existing structure and defects are studied and improved, and a micro-nano crystal polyhedron assembly, morphology control and assembly method based on spiroaromatic hydrocarbons is proposed. Summary of the invention

[0006] In view of the deficiencies in the prior art, the present invention provides a micro-nano crystal polyhedron assembly, morphology control and assembly method based on spiroaromatic hydrocarbons, which solves the problems raised in the above-mentioned background technology.

[0007] To achieve the above objectives, the present invention is implemented by the following technical solutions: a method for assembling, morphology regulating and assembling a micro-nano crystal polyhedron based on spiroaromatic hydrocarbons, wherein the micro-nano crystals are formed by orderly arrangement of spiroaromatic hydrocarbon molecules in a herringbone-like stacking pattern, wherein the molecular configuration of the spiroaromatic hydrocarbon molecules is that two cross-intersecting planes share a central carbon atom, and the morphology of the micro-nano crystals is a three-dimensional polyhedron, and the structural formula thereof is as follows:

[0008]

[0009] Furthermore, the preparation method includes the following steps: injecting the target compound dissolved in 1 mL THF solution at a concentration of 2 mM into 5 mL of vigorously stirred CTAB aqueous solution at a concentration of 2 mg / mL, stirring for 5 minutes, and standing for 24-72 hours to obtain polyhedral micro-nano crystals.

[0010] A certain mass of the target compound is dissolved in an organic solvent to prepare a solution with a concentration of 1-4 mM, and the target compound solution is injected into a vigorously stirred 2-4 mg / mL cationic surfactant aqueous solution, the volume ratio of the solution to the anionic surfactant aqueous solution is 1:5, stirred for 5-10 minutes, and allowed to stand at room temperature for 24-72 hours to obtain the polyhedral micro-nano crystals.

[0011] Furthermore, the organic solvent is tetrahydrofuran, dichloromethane or chlorobenzene.

[0012] Furthermore, the anionic surfactant is CTAB.

[0013] The polyhedral micro-nano crystals prepared by the above method have good crystallinity, and the simulation results are consistent with the experimental results.

[0014] Further, analysis of their structure-activity relationship showed that both molecules were stacked in a way that two adjacent molecules were antiparallel to form dimers, and the dimers were stacked in a fishbone pattern. The three-dimensional distribution of supramolecular forces ultimately led to a three-dimensional polyhedral crystal morphology. The SFX dimers were stacked only by weak van der Waals forces, while there were π...π and CH...π interactions between SDAFX dimers. SDAFX dimers showed stronger oriented stacking, which ultimately led to a more regular crystal morphology.

[0015] The present invention provides a micro-nano crystal polyhedron assembly, morphology regulation and assembly method based on spiroaromatic hydrocarbons, which has the following beneficial effects: the micro-nano crystal polyhedron assembly, morphology regulation and assembly method based on spiroaromatic hydrocarbons provides a technology for polyhedron assembly and morphology regularity regulation of micro-nano crystals based on spiroaromatic hydrocarbon molecules, adopts the traditional reprecipitation method, belongs to the category of green and environmentally friendly chemistry, obtains polyhedron micro-nano crystals with good crystallinity and uniform size, successfully regulates the morphology regularity of the polyhedron micro-nano crystals and explains the conformational relationship, further clarifies the role of SSH of SAHs in polyhedron self-assembly, and the realization of this strategy is also the key to the design of specific molecules and the regulation of assembly behavior. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 The single crystal structure, dimer stacking and supramolecular interaction quantitative analysis diagram of the SFX (upper) and SDAFX (lower) molecules of the present invention;

[0017] Figure 2 The morphology and structure characterization diagrams of SFX (upper) and SDAFX (lower) microcrystals of the present invention;

[0018] Figure 3 The growth morphology diagram of SFX and SDAFX organic crystals predicted by the software simulation of the present invention;

[0019] Figure 4 The stacking pattern and repeating unit diagram of SFX (top) and SDAFX (bottom) of the present invention. DETAILED DESCRIPTION

[0020] The following embodiments of the present invention are described in further detail in conjunction with the accompanying drawings and examples. The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0021] like Figure 1-Figure 4 As shown, the present invention provides a technical solution: a micro-nano crystal polyhedron assembly, morphology control and assembly method based on spiroaromatic hydrocarbons, wherein the micro-nano crystals are formed by orderly arrangement of spiroaromatic hydrocarbon molecules in a herringbone-like stacking, wherein the molecular configuration of the spiroaromatic hydrocarbon molecules is that two cross-intersecting planes share a central carbon atom, and the morphology of the micro-nano crystals is a three-dimensional polyhedron, and the structural formula thereof is as follows:

[0022]

[0023] The preparation method comprises the following steps: injecting a target compound dissolved in 1 mL of THF solution with a concentration of 2 mM into 5 mL of a vigorously stirred CTAB aqueous solution with a concentration of 2 mg / mL, stirring for 5 minutes, and standing for 24-72 hours to obtain polyhedral micro-nano crystals; dissolving a certain mass of the target compound in an organic solvent to prepare a solution with a concentration of 1-4 mM, injecting the target compound solution into a vigorously stirred cationic surfactant aqueous solution with a concentration of 2-4 mg / mL, wherein the volume ratio of the solution to the anionic surfactant aqueous solution is 1:5, stirring for 5-10 minutes, and standing for 24-72 hours at room temperature to obtain the polyhedral micro-nano crystals; the organic solvent is tetrahydrofuran. The polyhedral micro-nano crystals prepared by the above method have good crystallinity, and the simulation results are consistent with the experimental results. The structure-activity relationship is analyzed. The stacking of the two molecules is in accordance with the antiparallel formation of dimers by two adjacent molecules. The dimers are arranged in a herringbone pattern. The three-dimensional distribution of supramolecular forces ultimately leads to a three-dimensional polyhedral crystal morphology. The stacking of SFX dimers depends only on weak van der Waals forces, and there are π...π and CH...π interactions between SDAFX dimers. The SDAFX dimers show stronger oriented stacking, which ultimately leads to a more regular crystal morphology.

[0024] With SFX and SDAFX as target compounds, three-dimensional polyhedral structures were obtained by traditional reprecipitation method with tetrahydrofuran as good solvent and pure water as poor solvent at room temperature.

[0025] The material was obtained by reprecipitation:

[0026] The target compound dissolved in 1 mL of THF solution at a concentration of 2 mM was injected into 5 mL of a vigorously stirred CTAB aqueous solution at a concentration of 2 mg / mL, stirred for 5 minutes, and allowed to stand for 72 hours to obtain polyhedral micro-nano crystals.

[0027] Example 1

[0028] Experimental Methods of Nanoscale Self-Assembly of SFX and SDAFX Molecules

[0029] Weigh a certain mass of sample into a 10mL sample bottle, add 1mL of tetrahydrofuran to fully dissolve. Quickly inject the dissolved liquid into a sample bottle with a vigorous stirring magnet and 5mL of deionized water, cover the lid and stir for 5 minutes, remove the magnet, and let it stand for 72 hours to obtain a suspension of micro-nano crystals. Use a pipette to measure 20μL of the micro-nano crystal suspension and drop it on a clean and dry silicon wafer substrate. Allow the solvent to evaporate completely, and then observe and test it with a field emission scanning electron microscope at an accelerating voltage of 5kV and an emission current of 10μA.

[0030] Example 2

[0031] Molecular stacking structure-activity analysis of SFX and SDAFX

[0032] The arrangement of molecules on the a, b, and c axes was studied using MERCURY software. The stacking of the two molecules is based on the formation of dimers in the form of antiparallel adjacent molecules, and the dimers are arranged in a fishbone pattern. The stacking between SFX dimers relies only on weak van der Waals forces, while there are π...π and CH...π interactions between SDAFX dimers, and SDAFX dimers show stronger oriented stacking. Using Materials Studio 8.0 software, theoretical calculations were performed by inputting the single crystal parameters of the molecules to obtain the morphology of SFDBA and SFDBX crystals. Both the experimental results and the software analysis results clearly explain the molecular arrangement and crystal morphology. The three-dimensional distribution of the supramolecular forces of the two molecules ultimately leads to a three-dimensional polyhedral crystal morphology, and the SDAFX dimer shows a stronger oriented stacking, which ultimately leads to a more regular crystal morphology.

[0033] The embodiments of the present invention are given for the purpose of illustration and description, and are not intended to be exhaustive or to limit the invention to the disclosed forms. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments are selected and described in order to better illustrate the principles and practical applications of the present invention and to enable those of ordinary skill in the art to understand the present invention and thereby design various embodiments with various modifications suitable for specific uses.

Claims

1. A micro-nano crystal polyhedron assembly, morphology control and assembly method based on spiroaromatic hydrocarbons, characterized in that: The micro-nano crystals are formed by orderly arrangement of spiroaromatic molecules in a herringbone-like stacking. The molecular configuration of the spiroaromatic molecules is that two cross-planes share a central carbon atom. The morphology of the micro-nano crystals is a three-dimensional polyhedron, and its structural formula is as follows:

2. The method for assembling, morphology regulating and assembling micro-nano crystal polyhedrons based on spiroaromatic hydrocarbons according to claim 1, characterized in that: The preparation method comprises: dissolving a certain mass of a target compound in an organic solvent to prepare a solution with a concentration of 1-4 mM, injecting the target compound solution into a vigorously stirred anionic surfactant aqueous solution, stirring evenly for 5-10 minutes and then standing at room temperature to obtain the polyhedral micro-nano crystals.

3. The method for assembling, morphology regulating and assembling micro-nano crystal polyhedrons based on spiroaromatic hydrocarbons according to claim 2, characterized in that: The concentration of the anionic surfactant aqueous solution is 2-4 mg / mL.

4. The method for assembling, morphology regulating and assembling micro-nano crystal polyhedrons based on spiroaromatic hydrocarbons according to claim 3, characterized in that: The volume ratio of the target compound solution to the cationic surfactant aqueous solution is 1:

5.

5. The method for assembling, morphology regulating and assembling micro-nano crystal polyhedrons based on spiroaromatic hydrocarbons according to claim 4, characterized in that: The standing time at room temperature is 24-72h.

6. The method for assembling, morphology regulating and assembling micro-nano crystal polyhedrons based on spiroaromatic hydrocarbons according to claim 5, characterized in that: The organic solvent is any one of tetrahydrofuran, dichloromethane and chlorobenzene.

7. The method for assembling, morphology regulating and assembling micro-nano crystal polyhedrons based on spiroaromatic hydrocarbons according to claim 6, characterized in that: The cationic surfactant was CTAB.

8. The method for assembling, morphology regulating and assembling micro-nano crystal polyhedrons based on spiroaromatic hydrocarbons according to claim 7, characterized in that: The cross molecular configuration of spiroaromatic hydrocarbons enables the supramolecular forces on them to be distributed three-dimensionally in space, inducing the assembly of polyhedral morphologies.

9. The method for assembling, morphology regulating and assembling micro-nano crystal polyhedrons based on spiroaromatic hydrocarbons according to claim 8, characterized in that: Without changing the molecular configuration, the additional introduction of supramolecular forces will give it different SSH effects and further induce the regulation of its crystal morphology regularity.

10. The method for assembling, morphology regulating and assembling micro-nano crystal polyhedrons based on spiroaromatic hydrocarbons according to claim 9, characterized in that: The test was observed using a field emission scanning electron microscope at an accelerating voltage of 5 kV and an emission current of 10 μA.

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