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

Abstract

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.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1492647
Report Number(s):
LA-UR-15-24236
Journal ID: ISSN 0020-1669
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 54; Journal Issue: 16; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Myers, Thomas Winfield, Chavez, David E., Hanson, Susan Kloek, Scharff, Robert Jason, Scott, Brian Lindley, Veauthier, Jacqueline Marie, and Wu, Ruilian. Independent Control of Optical and Explosive Properties: Pyrazole–Tetrazine Complexes of First Row Transition Metals. United States: N. p., 2015. Web. doi:10.1021/acs.inorgchem.5b01313.
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Myers, Thomas Winfield, Chavez, David E., Hanson, Susan Kloek, Scharff, Robert Jason, Scott, Brian Lindley, Veauthier, Jacqueline Marie, & Wu, Ruilian. Independent Control of Optical and Explosive Properties: Pyrazole–Tetrazine Complexes of First Row Transition Metals. United States. https://doi.org/10.1021/acs.inorgchem.5b01313
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Myers, Thomas Winfield, Chavez, David E., Hanson, Susan Kloek, Scharff, Robert Jason, Scott, Brian Lindley, Veauthier, Jacqueline Marie, and Wu, Ruilian. Mon . "Independent Control of Optical and Explosive Properties: Pyrazole–Tetrazine Complexes of First Row Transition Metals". United States. https://doi.org/10.1021/acs.inorgchem.5b01313. https://www.osti.gov/servlets/purl/1492647.
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@article{osti_1492647,
title = {Independent Control of Optical and Explosive Properties: Pyrazole–Tetrazine Complexes of First Row Transition Metals},
author = {Myers, Thomas Winfield and Chavez, David E. and Hanson, Susan Kloek and Scharff, Robert Jason and Scott, Brian Lindley and Veauthier, Jacqueline Marie and Wu, Ruilian},
abstractNote = {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.},
doi = {10.1021/acs.inorgchem.5b01313},
journal = {Inorganic Chemistry},
number = 16,
volume = 54,
place = {United States},
year = {Mon Aug 03 00:00:00 EDT 2015},
month = {Mon Aug 03 00:00:00 EDT 2015}
}
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