Coordination Competition Strategy for Constructing High-Energy Photosensitive Complexes
High-dimensional energetic coordination compounds (ECCs) exhibit high stability and low sensitivity owing to their complex network structure, making them valuable in functional energetic materials such as combustion catalysis and insensitive detonating explosives. Four ECCs, [Co(DNBT)(H<sub>2</sub>O)<sub>4</sub>]<i><sub>n</sub></i> (ECC-1), [Ni(DNBT)(H<sub>2</sub>O)<sub>4</sub>] (ECC-2), [Cu<sub>2</sub>(DNBT)<sub>2</sub>(H<sub>2</sub>O)<sub>3</sub>MeOH] (ECC-3), and [Zn(DNBT)(H<sub>2</sub>O)<sub>4</sub>] (ECC-4), were synthesized by modifying the metal centers and using 5,5'-dinitro-4<i>H</i>,4'<i>H</i>-3,3'-bi(1,2,4-triazole) (DNBT) as ligands. After changing the solution environment and adding the auxiliary ligand 4<i>H</i>-1,2,4-triazol-4-amine (4-ATr), we obtained three ECCs with similar coordination structures once again: [Co<sub>2</sub>(DNBT)<sub>2</sub>(4-ATr)<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub>] (ECC-5), [Ni<sub>2</sub>(DNBT)<sub>2</sub>(4-ATr)<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub>] (ECC-6), and [Cu<sub>2</sub>(DNBT)<sub>2</sub>(4-ATr)<sub>3</sub>] (ECC-7). ECCs with fewer water molecules were chosen for laser ignition and detonation tests to evaluate their laser-induced ignition and detonation capabilities, indicating potential applications as laser initiators. The laser response behavior differs between [Co<sub>2</sub>(DNBT)<sub>2</sub>(4-ATr)<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub>] and [Cu<sub>2</sub>(DNBT)<sub>2</sub>(4-ATr)<sub>3</sub>]. [Cu<sub>2</sub>(DNBT)<sub>2</sub>(4-ATr)<sub>3</sub>] exhibits excellent laser response, with a low minimum laser initiation energy of 11 mJ and a short lengthy ignition delay of 2.31 ms, whereas [Co<sub>2</sub>(DNBT)<sub>2</sub>(4-ATr)<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub>] is less sensitive under the same conditions. Theoretical calculations and tests at different laser power densities indicate that [Co<sub>2</sub>(DNBT)<sub>2</sub>(4-ATr)<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub>] possesses more efficient photothermal conversion. This reduced sensitivity to laser response may stem from the presence of water. The charge transfer behavior between these compounds is thoroughly analyzed through theoretical and structural studies.
Authors
- Changgen Feng (ORCID: https://orcid.org/0000-0003-1265-7213)
- Quancheng Liu (ORCID: https://orcid.org/0000-0001-9552-1738)
- Rufang Peng (ORCID: https://orcid.org/0000-0002-2517-0853)
- Hu Deng (ORCID: https://orcid.org/0000-0002-5889-1630)
- Juan Shen (ORCID: https://orcid.org/0000-0003-2797-9266)
- Wenjia Hao (ORCID: https://orcid.org/0000-0001-6732-0509)
- Jinsong Li (ORCID: https://orcid.org/0009-0009-9988-0602)
- Dan Xu (ORCID: https://orcid.org/0000-0003-1753-3594)
- Bo Jin (ORCID: https://orcid.org/0000-0002-6966-2876)
- Ting Zhang (ORCID: https://orcid.org/0000-0002-9066-5625)
Institutions
- Beijing Institute of Technology (CN)
- Southwest University of Science and Technology (CN)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2025-02-20
- DOI
- https://doi.org/10.1021/acs.inorgchem.4c04650
- Citations
- 3
- Primary Topic
- Free Radicals and Antioxidants
- Type
- article
- Field-Weighted Citation Impact
- 2.81
Funders
- National Natural Science Foundation of China