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Published on: October 31, 2017
Independent Control of Optical and Explosive Properties: Pyrazole-Tetrazine Complexes of First Row Transition Metals
Thomas W Myers1, David E Chavez1, Susan K Hanson1
1†M Division, ‡Chemistry Division, §Materials Physics and Applications, and ∥Bioscience Division, Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, New Mexico 87545, United States.
Abstract:
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 Fe(II)(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 Cu(II)(NO3)2·5/2H2O to form [(RTzDMP)2Cu(NO3)][NO3] (R = NH2 (7), DNAZ (8)) in addition to reacting with Cu(I)(CH3CN)4(PF6) to form [(RTzDMP)2Cu][PF6] (R = NH2 (9), DNAZ (10)). Lastly 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.
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