CN110437822A - One kind being based on the supermolecule white light emitting material and preparation method thereof of column [5] aromatic hydrocarbons - Google Patents

Abstract

It is by the equal benzene trimethamide of column [5] aromatic hydrocarbons and 4-aminopyridine functionalization, heating is sufficiently dissolved into DMSO-H the invention discloses a kind of supermolecule white light emitting material for being based on column [5] aromatic hydrocarbons₂Clear solution is obtained in O mixed system, is cooled to room temperature to form stable supramolecular hydrogel, naturally dry forms supermolecule xerogel.The present invention using column [5] aromatic hydrocarbons TP there is good electron rich cavity and the equal benzene trimethamide Q of 4-aminopyridine functionalization to have electron deficient, in DMSO-H₂In O mixed system, stable supramolecular hydrogel TP-Q is formed by interactions such as hydrogen bond, C-H ... π, exterior wall π-π, hydrogel TP-Q naturally dry forms xerogel；And xerogel shows the fluorescent emission of white, can be used for preparing various optical devices.

Description

A kind of supramolecular white light material based on pillar[5]arene and preparation method thereof

technical field

The invention relates to a new type of supramolecular hydrogel TP-Q, in particular to a supramolecular hydrogel with the functions of hydrogen bonds, C-H...π and external wall π-π; the invention also relates to the supramolecular hydrogel The glue shows white fluorescence emission in the state of dry powder, and is used as a white light material; the white light material can be applied in many optical materials, and belongs to the field of supramolecular material research.

Background technique

White light-emitting materials have attracted extensive attention due to their potential applications in fluorescent display media and optical devices. Typically, the generation of white light emission relies on the simultaneous emission of the three primary RGB (red, green and blue) colors, at least two complementary colors or modulation of different metals, thus spanning the entire visible spectrum. There are many approaches to develop efficient white light emitting systems, such as nanoparticles, small molecules, polymers, quantum dots, metal-organic frameworks, and assemblies. With the rapid development of supramolecular chemistry, new opportunities are provided for the construction of white light emitting materials based on supramolecular assembly methods.

As a new generation of supramolecular macrocyclic compounds, pillararenes have demonstrated novel effects in fluorescence detection. Many ion detection systems have been well developed by modifying the pillararene structure. The supramolecular polymer hydrogel based on pillar arene is a good fluorescent material. Therefore, new supramolecular white light materials can be designed and synthesized by taking advantage of its electron-rich cavity and good fluorescent properties.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a preparation method of a supramolecular white light material based on pillar [5] arene.

1. Preparation of supramolecular white light materials based on pillar[5]arene

The supramolecular white light material based on the pillar [5] arene of the present invention is a trimesic acid amide (marked as Q) functionalized with the pillar [5] arene (marked as TP) and 4-aminopyridine, and fully dissolved in DMSO- A transparent solution was obtained in the H ₂ O mixed system, cooled to room temperature to form a stable supramolecular hydrogel, and naturally dried to form a supramolecular xerogel, which was marked as TP-Q.

The structural formula of column[5]arene (TP) is:

4-Aminopyridine functionalized trimesic acid amide (Q) is:

The structural formula of the supramolecular hydrogel TP-Q is:

The molar ratio of column[5] arene and 4-aminopyridine functionalized trimesic acid amide is 3:1 ~ 3.5:1.

Column[5] The mass-volume ratio of the mixture system of aromatic hydrocarbon (TP) and 4-aminopyridine functionalized trimesamide (Q) and DMSO-H ₂ O was 45-50 mg/mL.

In the DMSO-H ₂ O mixed system, the volume ratio of DMSO to H ₂ O was 1.5:1~2:1.

2. Structure and properties of supramolecular white light materials

Figure 1 is a ¹ HNMR titration chart of TP, Q and TP-Q. In the ¹ H NMR titration, Ha, Hb and Hc on the column[5]arene TP all moved downfield, while H1, H4 on the 4-aminopyridine functionalized trimesamide Q moved downfield, H2 Moving to the high field indicates that the interaction between TP and Q is through hydrogen bonding and CH…π, and the pyridine ring part of Q enters the cavity of the pillar[5]arene TP.

Figure 2 shows the IR spectra of TP, Q and TP-Q. In the IR spectrum, the stretch vibration peak of -NH on Q moves from 3438 cm ^-1 to 3425 cm ^-1 , and the stretching vibration peak of methoxy-OCH _on TP moves from 1208 cm ^-1 to 1086 cm ^-1 , further It shows that the interaction between TP and Q is through hydrogen bonding.

Figure 3 is a scanning electron microscope image of TP, Q and TP-Q. Among them, a, b, c, d are SEM images of TP, Q, TP-Q and TEM images of TP-Q, respectively. It can be seen from the scanning electron microscope image that the electron microscope of TP shows a regular polyhedron shape, the electron microscope of Q shows a regular rod shape, and the electron microscope of TP-Q shows a porous shape. The SEM images further support the above experimental results.

Figure 4 is an electrostatic surface potential (ESP) plot of TP, Q and TP-Q. In electrostatic surface potential (ESP), the pillar[5]arene TP appears red, the 4-aminopyridine-functionalized trimesamide Q appears yellow-green, and TP-Q appears yellow, further indicating that the pyridine ring moiety of Q enters the into the cavity of the column[5]arene TP, which reduces the electron-richness of the column[5]arene TP, showing a yellow color.

Figure 5 is a graph of the reduced density gradient (RDG) of the interaction of TP and Q. It can be seen that there is a weak interaction between TP and Q in the decreasing density gradient (RDG).

Figure 6 is an independent gradient model (IGM) diagram of the interaction between TP and Q. From the IGM, it can be seen that there are hydrogen bonds and C-H...π interactions between TP and Q. The weak interaction between TP and Q was further verified by independent gradient model (IGM).

FIG. 7 is the fluorescence spectra of TP, Q and TP-Q. It can be seen from Figure 7 that the fluorescence of TP-Q is different from that of TP and Q, and the fluorescence of TP-Q is located in the white light emission region.

FIG. 8 is a CIE graph of TP, Q and TP-Q. The CIE coordinates of TP-Q calculated from the CIE coordinates are (0.29, 0.29), which are very close to the CIE coordinates of pure white emission.

To sum up, the present invention relates to the synthesis of a novel supramolecular white light material, which utilizes the pillar[5]arene TP with a good electron-rich cavity, and the 4-aminopyridine-functionalized trimesicamide Q with a deficiency. Electronic, in the DMSO-H ₂ O mixed system, a stable supramolecular hydrogel TP-Q is formed through hydrogen bonding, CH…π, outer wall π-π and other interactions, and the hydrogel TP-Q is naturally dried. Xerogels are formed; the xerogels exhibit white fluorescence emission and can be used to prepare various optical devices.

Description of drawings

Figure 1 is a ¹ HNMR titration chart of TP, Q and TP-Q.

Figure 2 shows the IR spectra of TP, Q and TP-Q.

Figure 3 is a scanning electron microscope image of TP, Q and TP-Q.

Figure 4 is an electrostatic surface potential (ESP) plot of TP, Q and TP-Q.

Figure 5 is a graph of the reduced density gradient (RDG) of the interaction of TP and Q.

Figure 6 is an independent gradient model (IGM) diagram of the interaction between TP and Q.

FIG. 7 is the fluorescence spectra of TP, Q and TP-Q.

FIG. 8 is a CIE graph of TP, Q and TP-Q.

Detailed ways

The preparation and properties of a novel supramolecular white light material TP-Q of the present invention are further described below through specific examples.

1. Synthesis of column [5] Aromatic Hydrogel Factor TP: In a 250ml round bottom flask, add 1,4-dimethoxybenzene (1.38g, 10mmol), 1,2-dichloroethane (200ml) , paraformaldehyde (0.64 g, 20 mmol), and the mixture was stirred at 30 °C for 30 min. Boron trifluoride diethyl etherate (2.5 ml, 16.5 mmol) was then added to the solution, and the mixture was stirred at room temperature for 1 hour and concentrated by rotary evaporation. The resulting oil was dissolved in _CH2Cl2 and washed ₃ times with _H2O . The organic layer was dried over anhydrous Na ₂ SO ₄ and evaporated to give crude product which was separated by flash column chromatography using petroleum ether/dichloromethane (2:1, v/v) as a white solid TP, yield For: 52%.

2. Synthesis of 4-aminopyridine-functionalized trimesic acid gel factor Q: add 4-aminopyridine (0.75 g, 8.0-8.05 mmol) and CHCl ₃ ((40 ml) to a 100 ml round-bottomed flask, Add trimesic acid chloride (0.52 g, 5.0 ~ 5.05 mmol) and CHCl ₃ (40 ml) to the constant pressure funnel, and slowly drop them into the round-bottomed flask overnight; suction filtration to obtain a white solid Q in the yield of : 80%.

3. Preparation of white light material: Weigh TP (0.023 mmol, 0.01 g) and Q (0.013 mmol, 0.01 g) and add them to 300 μl of DMSO and 200 μl of H ₂ O, and fully dissolve them under heating to obtain a transparent solution ; When cooled to room temperature, the solution forms a stable supramolecular hydrogel, and the supramolecular hydrogel is naturally dried to obtain the supramolecular white light material TP-Q. Its CIE coordinate diagram is shown in Figure 8.

Claims (4)

1. A preparation method of a supramolecular white light material based on pillar [5] aromatic hydrocarbon is to fully dissolve the trimesic acid amide functionalized with pillar [5] aromatic hydrocarbon and 4-aminopyridine into a DMSO-H ₂ O mixed system by heating A transparent solution is obtained, cooled to room temperature to form a stable supramolecular hydrogel, and naturally dried to form a supramolecular xerogel; The structural formula of the column [5] aromatic hydrocarbon is: The structural formula of 4-aminopyridine functionalized trimesic acid amide is: . 2. the preparation method of the supramolecular white light material based on pillar [5] aromatic hydrocarbons as claimed in claim 1, is characterized in that: the mol ratio of the trimesic amide of pillar [5] aromatic hydrocarbon and 4-aminopyridine functionalization is 3: 1 to 3.5:1. 3. The preparation method of the supramolecular white light material based on pillar [5] aromatic hydrocarbons as claimed in claim 1, it is characterized in that: trimesic acid amide and DMSO-H ₂ O functionalized with pillar [5] aromatic hydrocarbon and 4-aminopyridine The mass-volume ratio of the mixed system was 45-50 mg/mL. 4. the preparation method of the supramolecular white light material based on pillar [5] aromatic hydrocarbon as claimed in claim 1, is characterized in that: in DMSO-H ₂ O mixed system, the volume ratio of DMSO and H ₂ O is 1.5:1～2 :1.