CN-121991364-A - Cage-shaped trinuclear pyrazole cuprous energetic complex with ultrahigh thermal stability and synthesis method thereof

Abstract

The invention discloses a cage-shaped trinuclear pyrazole cuprous energetic complex with ultrahigh thermal stability and a synthesis method thereof, and the energetic complex is applied to energetic materials. According to the invention, 3-nitropyrazole and copper nitrate are mixed, and a cage-shaped trinuclear pyrazole cuprous energetic complex is synthesized through self-assembly, and the triangle-shaped stable pi-pi stacking structure has high density, good thermal stability and low sensitivity, and is not oxidized into bivalent copper in air after long-time storage.

Inventors

• HUANG WEI
• HUANG WENZHE
• TANG YONGXING

Assignees

• 南京理工大学

Dates

Publication Date

20260508

Application Date

20241107

Claims (8)

1. 1. The caged trinuclear pyrazole cuprous energetic complex with ultrahigh thermal stability is characterized by comprising the following structure:
2. 2. The caged trinuclear cuprous pyrazole energetic complex according to claim 1, wherein the unit cell parameters are as follows: α= 92.716 (4) °, β= 97.813 (3) °, γ= 105.297 (3) °, z=2, unit cell volume
3. 3. A method for synthesizing the caged trinuclear pyrazole cuprous energetic complex according to claim 1 or 2, comprising the steps of mixing 3-nitropyrazole with copper nitrate, synthesizing the caged trinuclear pyrazole cuprous energetic complex by self-assembly,
4. 4. A method according to claim 3, characterized in that it comprises in particular the following steps: Dispersing 3-nitropyrazole in a reaction solvent at a certain temperature, adding copper nitrate trihydrate, carrying out ultrasonic treatment, reacting in a reaction kettle at a certain temperature, naturally cooling, centrifuging, filtering, washing and drying to obtain the caged trinuclear pyrazole cuprous energetic complex.
5. 5. The method of claim 3 or 4, wherein the reaction temperature is 90 ℃ to 100 ℃.
6. 6. The method according to claim 3 or 4, wherein the reaction solvent is a mixed solvent of water, methanol and N, N-dimethylformamide in a volume ratio of 1:1:1.
7. 7. The method according to claim 3 or 4, wherein the reaction time is 10 to 14 hours.
8. 8. Use of a caged trinuclear cuprous pyrazole energetic complex according to claim 1 or 2 as an initiating explosive.

Description

Cage-shaped trinuclear pyrazole cuprous energetic complex with ultrahigh thermal stability and synthesis method thereof Technical Field The invention belongs to the field of energetic materials, and particularly relates to a preparation method of an energetic metal organic framework crystal material (Cu-MOF) self-assembled by Cu (NO 3)2 and 3-nitropyrazole), which is expected to have good application prospect in the field of heat-resistant energetic materials. Background The research of the metal complex is one of the development fronts of modern inorganic chemistry, namely, metal ions are used as nodes, organic ligands are used as connecting bodies, the geometric coordination nodes with changeable metal ions and the symmetry of the organic ligands are utilized, and the interesting topological structure obtained by assembling under proper conditions is a new-stage product of supermolecular chemistry development and is also an important field of crystal engineering. Because of its unique structure, adjustable properties and potential application value in chemical fields, metal coordination polymers have attracted extensive attention in the fields of coordination chemistry and material science, and are expected to be applied to the fields of sensors, gas storage, magnetic materials, energetic materials and the like. Notably, the high density, good thermal stability and low sensitivity of metal coordination polymers have led to increased attention in the field of energetic materials. The synthesis of metal coordination polymers of triazolotriazines coordinated with Cu (NO 3)2) has been reported by ZhiwenYe et al (New J.chem.,2024,48,16331-16336), but in the form of ionic salts coordinated with oxygen, and did not form a stable cage-like framework. Disclosure of Invention The invention aims to provide an energetic metal coordination compound synthesized by one pot based on a hydrothermal method and a method thereof, wherein the compound has a triangular-prism cage-shaped stable structure and an attraction pi-pi stacking structure between metal cations. The compound has stronger heat stability. In a first aspect, the invention provides a caged trinuclear cuprous pyrazole energetic complex (Cu-MOF) with ultrahigh thermal stability, which has the following structure: Preferably, the unit cell parameters of the caged trinuclear cuprous pyrazole energetic complex are as follows: α= 92.716 (4) °, β= 97.813 (3) °, γ= 105.297 (3) °, z=2, unit cell volume In a second aspect, the invention provides a method for synthesizing the caged trinuclear pyrazole cuprous energy-containing complex in the first aspect, which comprises the steps of mixing 3-nitropyrazole with copper nitrate, synthesizing the triangular prism caged cuprous complex through self-assembly, Preferably, the method specifically comprises the following steps: Dispersing 3-nitropyrazole in a reaction solvent at a certain temperature, adding copper nitrate trihydrate, carrying out ultrasonic treatment, reacting in a reaction kettle at a certain temperature, naturally cooling, centrifuging, filtering, washing and drying to obtain the Cu-MOF. Preferably, the reaction temperature may be 90 ℃ to 100 ℃. Preferably, the reaction solvent is a mixed solvent of water, methanol and N, N-dimethylformamide in a volume ratio of 1:1:1. Preferably, the reaction time may be 10 to 14 hours. In a third aspect, the invention provides a use of the caged trinuclear cuprous pyrazole energetic complex of the first aspect as an initiating explosive. Compared with the prior art, the invention has the remarkable advantages that the invention synthesizes the cage-shaped trinuclear cuprous pyrazole energetic complex with a pi-pi stacking structure between metal cations and stable structure, the complex has high density, good thermal stability and low sensitivity, is not oxidized into bivalent copper in the air for long-time storage, and is expected to synthesize energetic materials with good application value by further adding energetic molecules in the structure. Drawings FIG. 1 is a crystal structure diagram of a caged trinuclear cuprous pyrazole energetic complex (Cu-MOF). FIG. 2 is a diagram of a crystal sample of a caged trinuclear cuprous pyrazole energetic complex (Cu-MOF). FIG. 3 is a simulated XRD pattern of a caged trinuclear cuprous pyrazole energetic complex (Cu-MOF). FIG. 4 is a measured XRD pattern of a caged trinuclear cuprous pyrazole complex (Cu-MOF). FIG. 5 is a DSC of a caged trinuclear cuprous pyrazole energetic complex (Cu-MOF). Detailed Description The invention will be further described with reference to the drawings and the specific examples. Example 1 3Mmol (339 mg) of 3-nitropyrazole was dispersed in 50mL of a polytetrafluoroethylene liner filled with 2mL of water, 2mL of methanol, 2mL of mixed solvent of LDMF (N, N-dimethylformamide) at room temperature, followed by adding 3mmol (723 mg) of copper nitrate trihydrate at a time, followed by ultrasonic treatment