CN114507357A - Hexamercapto-silver benzene coordination polymer and preparation method thereof - Google Patents

Abstract

The invention discloses a hexamercapto silver phenyl coordination polymer and a preparation method thereof. In an inert atmosphere, reacting hexamercaptobenzene with silver oxide in an organic solvent I to obtain a first hexamercaptosilver benzene coordination polymer, and reacting the hexamercaptosilver benzene coordination polymer with nitrosyl tetrafluoroborate in an organic solvent II to obtain a second hexamercaptosilver benzene coordination polymer. The two hexamercaptobenzene silver coordination polymers provided by the invention have good crystallinity and high conductivity, solve the problems that the preparation steps are complex and the coordination polymer with high conductivity and high crystallinity cannot be obtained in the prior art, and have important significance for developing organic electronic materials.

Description

Hexamercapto-silver benzene coordination polymer and preparation method thereof

Technical Field

The invention relates to a hexamercapto silver phenyl coordination polymer and a preparation method thereof, belonging to the field of organic electronic materials.

Background

In the last decade, the conductive coordination polymer has attracted people's attention and research with the advantages of adjustable photoelectric properties, large-scale solution processing capability, good mechanical flexibility and the like, and has gained important application in the fields of electronics and optoelectronics. Due to the adjustability of the structure and function, the conductive coordination polymer has great application potential in the fields of electrocatalysts, supercapacitors, thermoelectric devices and the like, and becomes one of the hot topics in the research field of current electronic materials.

In the search for coordination polymers, hexametaphosphate coordination polymers have been extensively studied for their excellent electrical transport properties, especially hexametaphosphate silver coordination polymers. However, the synthesis of such polymers mostly relies on complex interfacial synthesis, the reaction times are long, and the yields and phase purities are often less than ideal and not suitable for large-scale commercial applications. Therefore, the exploration of a simple and controllable method with good phase purity and more suitability for laboratory and commercial production and preparation is very key to the development of conductive materials. Based on the particularity of the metal oxide in the coordination assembly reaction, further research on the synthesis method of the metal oxide is necessary.

Disclosure of Invention

The invention aims to provide a coordination polymer with high crystallinity and conductivity so as to provide more selective paths for organic semiconductor materials; meanwhile, the invention also provides a simple and efficient preparation method of the coordination polymer, which can obtain an electronic material with good phase purity under the condition of one pot and has important significance for developing a coordination polymer material with high conductivity.

The first hexamercapto silver benzene coordination polymer provided by the invention has a chemical formula of Ag₅BHT is prepared by the following steps:

reacting hexa-mercapto benzene with silver oxide in an organic solvent I under inert atmosphere to obtain the silver oxide.

In the preparation method, the organic solvent I is isopropanol, ethanol or n-propanol.

In the preparation method, the reaction temperature is 50-80 ℃, and the reaction time is 12-24 hours.

In the above preparation method, the molar ratio of the silver oxide to the hexamercaptobenzene is 1.5-2.5: l, more preferably 2.5: 1.

in the above preparation method, the method further comprises the following steps after the reaction is finished:

and washing the product obtained after the reaction system is filtered by adopting water, methanol and acetone in sequence, and washing at least twice.

The chemical formula of the second hexamercapto silver benzene coordination polymer provided by the invention is Ag₃BHT is prepared by the following steps:

and (3) reacting the first hexamercaptosilver coordination polymer with nitrosyl tetrafluoroborate in an organic solvent II to obtain the product.

In the preparation method, the organic solvent II is acetonitrile, benzonitrile or N, N-dimethylacetamide;

the reaction temperature is 10-50 ℃, and the reaction time is 12-24 h.

In the preparation method, the molar ratio of the nitrosyl tetrafluoroborate to the silver hexametaphosphate coordination polymer is 4-6: 1;

the method also comprises the following processing steps after the reaction is finished:

and washing the product obtained after the reaction system is filtered by adopting water, methanol and acetone in sequence, and washing at least twice.

The crystallographic structure parameters of the two hexamercaptobenzene silver coordination polymers prepared by the invention are shown in table 1 (obtained by combining powder X-ray diffraction and three-dimensional rotating electron diffraction technical analysis):

as can be seen from the data in table 1, the two materials prepared have completely different crystal systems and space groups, which results in differences in the electrical transport properties of the resulting materials.

TABLE 1 Ag₅BHT and Ag₃Crystallographic structure of BHT

The invention has the following beneficial technical effects:

(1) the raw materials and the solvent have wide sources, low toxicity and no harm, and the method is a novel method for preparing the material which is green and can be developed sustainably.

(2) The reaction process is simple and controllable, the yield is high, and the method is more suitable for laboratory and commercial production and preparation.

(3) The prepared material has good crystallinity and phase purity, high conductivity and adjustable electrical transport performance.

Drawings

FIG. 1 is a flow chart for preparing Ag-BHT electronic materials.

FIG. 2 shows Ag₅Powder X-ray diffraction pattern (XRD) of BHT and its comparison with theoretical.

FIG. 3 is Ag₃Powder X-ray diffraction pattern (XRD) of BHT and its comparison with theoretical.

Fig. 4 is a graph comparing powder X-ray diffraction patterns (XRD) of products obtained by reacting different equivalent amounts of silver oxide with BHT.

FIG. 5 Ag after briquetting₅Conductivity curve of BHT electronic materialA wire.

FIG. 6 Ag after briquetting₃The conductivity curve of BHT electronic material.

Detailed Description

The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.

Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.

First, solvent degassing

60ml of isopropyl alcohol was charged into a 100ml two-necked flask, and dissolved oxygen in the solvent was removed by the Freeze-Thaw method using liquid nitrogen.

Second, the preparation process

1) Under the protection of argon, adding 0.1g of hexamercaptobenzene (0.37 mmol) and 0.2g of silver oxide (0.92 mmol) into 60mL of degassed isopropanol, raising the temperature of the reaction solution to 60 ℃, reacting for 24 hours, naturally cooling the reaction solution to room temperature, filtering, washing with water, methanol, acetone and ether in sequence, drying in a vacuum drying oven (absolute pressure of 0.05Pa) at 80 ℃ for 24 hours to obtain a first hexamercaptobenzene-silver coordination polymer, and marking as Ag₅BHT。

2) Dispersing the product prepared in the step 1) in acetonitrile, adding nitrosyl tetrafluoroborate (0.09g, 0.74mmol), reacting at room temperature for 24h, filtering, washing with water, acetonitrile and diethyl ether in sequence, and drying in a vacuum drying oven (absolute pressure of 0.05Pa) at 80 ℃ for 24h to obtain a second silver hexamercaptobenzene coordination polymer marked as Ag₃BHT。

Characterization and testing of three, Ag-BHT

The prepared Ag-BHT is respectively used for the characterization of powder X-ray diffraction, element analysis, inductively coupled plasma spectrometer and the like, and the conductivity test is carried out after the pressing block (2X 5mm, at-1 GPa).

For Ag₅Characterization of BHT conductive coordination polymer materials: theoretical element content of the material: c, 8.97; s, 23.93; ag, 67.10; experimental element content of the material: c, 9.12; s, 23.32; ag,67.43, indicating that Ag with high phase purity can be obtained by using silver oxide as a reaction precursor₅BHT。

For Ag₃Characterization of BHT conductive coordination polymer materials: theoretical element content of the material: c, 12.26; s, 32.71; ag, 55.03; experimental element content of the material: c, 11.13; s, 33.12; ag,55.51, indicating nitrosyl oxidation of Ag by tetrafluoroboric acid₅BHT derived Ag₃BHT has high phase purity.

FIG. 1 is Ag₅BHT and Ag₃BHT synthesis scheme.

FIG. 2 is Ag prepared₅The powder XRD pattern of the BHT material, from which it can be seen that the experimental XRD (upper curve) and the simulated XRD (lower curve) are highly consistent, with the narrow half-width, sharp and well-separated peaks observed in the XRD spectra demonstrating its high crystallinity.

FIG. 3 is Ag prepared₃From the powder XRD pattern of the BHT material, it can be seen that the experimental XRD (upper curve) and the simulated XRD (lower curve) fit well, with the peak corresponding to the ab-plane of the structure, the broad peak corresponding to the c-axis of the structure, and the broadening of the c-axis reflection peak due to the intrinsic anisotropy of the plate-like crystals.

FIG. 4 is a comparison of XRD patterns of the product obtained when 1 equivalent of silver oxide (upper curve) and 2.5 equivalents of silver oxide (lower curve) were charged, and it is apparent that there is a difference in XRD diffraction peak position and half-value width, that is, when a small amount of silver oxide was charged, the desired Ag could not be obtained₅BHT product.

Fig. 5 and 6 are graphs of the conductivity of Ag-BHT after briquetting. It can be seen from the figure that the electrical conductivity of both materials increases with increasing temperature, at 400K, Ag₅The electrical conductivity of BHT can reach 24S/cm, Ag₃The BHT has the conductivity of 0.00038S/cm, so that two organic electronic materials with adjustable conductivity can be obtained based on two different preparation methods.

Claims (10)

1. A preparation method of a hexamercaptobenzene silver coordination polymer comprises the following steps:

reacting hexa-mercapto benzene with silver oxide in an organic solvent I under inert atmosphere to obtain the silver oxide.

2. The method of claim 1, wherein: the organic solvent I is isopropanol, ethanol or n-propanol.

3. The production method according to claim 1 or 2, characterized in that: the reaction temperature is 50-80 ℃, and the reaction time is 12-24 h.

4. The production method according to any one of claims 1 to 3, characterized in that: the molar ratio of the silver oxide to the hexamercaptobenzene is 1.5-2.5: l.

5. The production method according to any one of claims 1 to 4, characterized in that: the method also comprises the following processing steps after the reaction is finished:

and washing the filtered product of the reaction system by adopting water, methanol and acetone in sequence.

6. A hexamercaptobenzene silver coordination polymer made by the process of any one of claims 1 to 5.

7. A preparation method of a hexamercaptobenzene silver coordination polymer comprises the following steps:

the silver hexametaphosphate coordination polymer of claim 6 is reacted with nitrosyl tetrafluoroborate in an organic solvent II to obtain the product.

8. The method of claim 7, wherein: the organic solvent II is acetonitrile, benzonitrile or N, N-dimethylacetamide;

the reaction temperature is 10-50 ℃, and the reaction time is 12-24 h.

9. The production method according to claim 7 or 8, characterized in that: the molar ratio of the nitrosyl tetrafluoroborate to the silver hexametaphosphate coordination polymer is 4-6: 1;

the method also comprises the following processing steps after the reaction is finished:

and washing the filtered product of the reaction system by adopting water, methanol and acetone in sequence.

10. A hexamercaptobenzene silver coordination polymer made by the process of any one of claims 7-9.

Images