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Title: Independent Control of Optical and Explosive Properties: Pyrazole–Tetrazine Complexes of First Row Transition Metals

Journal Article · · Inorganic Chemistry
 [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
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In this study, complexes of 3-amino-6-(3,5-dimethylpyrazole)tetrazine) (NH2TzDMP, 1) and 3-(3,3'-dinitroazetidine)-6-(3,5-dimethylpyrazole)tetrazine) (DNAZTzDMP, 2) with first row transition metal centers were synthesized. Reactions of FeII(H2O)6(BF4)2 and Fe(NO3)3·9H2O with 1 and 2 both led to complexes of the form [(RTzDMP)3Fe]X2 (X = BF4, R = NH2 (3), DNAZ (4); X = NO3, R = NH2 (5), DNAZ (6)), which showed intense MLCT bands in the visible region of the spectrum. Ligands 1 and 2 also reacted with CuII(NO3)2·5/2H2O to form [(RTzDMP)2Cu(NO3)][NO3] (R = NH2 (7), DNAZ (8)) in addition to reacting with CuI(CH3CN)4(PF6) to form [(RTzDMP)2Cu][PF6] (R = NH2 (9), DNAZ (10)). Finally, reactions of 1 and 2 with Co(NO3)2·6H2O and Ni(NO3)2·6H2O led to [(NH2TzDMP)2Co(H2O) (NO3)][NO3] (11), [(DNAZTzDMP)2Co(H2O)2][NO3]2 (12), [(NH2TzDMP)3Ni][NO3]2 (13), and [(DNAZTzDMP)2Ni(H2O)2][NO3]2 (14). The complexes display rich electrochemical and photophysical properties that are unaffected by derivation with explosive groups.

Research Organization:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Laboratory Directed Research and Development (LDRD) Program
Grant/Contract Number:
89233218CNA000001
OSTI ID:
1492647
Report Number(s):
LA-UR-15-24236
Journal Information:
Inorganic Chemistry, Vol. 54, Issue 16; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 17 works
Citation information provided by
Web of Science

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Cited By (7)

2-Methyl-substituted monotetrazoles in copper( ii ) perchlorate complexes: manipulating coordination chemistry and derived energetic properties journal January 2019
New green energetic materials based on unsymmetrically substituted pyrazole-tetrazines and their hydroperchlorates journal January 2019
Synthesis and Characterization of Tetrahedral Zinc(II) Complexes with 3, 6,7-Triamino-7 H -[1, 2,4]triazolo[4, 3- b ][1, 2,4]triazole as Nitrogen-Rich Ligand : Synthesis and Characterization of Tetrahedral journal February 2016
Azido and Tetrazolo 1,2,4,5-Tetrazine N-Oxides journal February 2017
Synthesis and Electrochemical Behavior of Electron-Rich s-Tetrazine and Triazolo-tetrazine Nitrate Esters journal June 2016
Highly functional energetic complexes: stability tuning through coordination diversity of isomeric propyl-linked ditetrazoles journal January 2018
Maximization of the energy capability level in transition metal complexes through application of 1-amino- and 2-amino-5 H -tetrazole ligands journal January 2018

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY