Independent Control of Optical and Explosive Properties: Pyrazole鈥揟etrazine Complexes of First Row Transition Metals

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• 作者：Thomas W. Myers ; David E. Chavez ; Susan K. Hanson ; R. Jason Scharff ; Brian L. Scott ; Jacqueline M. Veauthier ; Ruilian Wu
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：August 17, 2015
• 年：2015
• 卷：54
• 期：16
• 页码：8077-8086
• 全文大小：595K
• ISSN：1520-510X

文摘

Complexes of 3-amino-6-(3,5-dimethylpyrazole)tetrazine) (NH₂TzDMP, 1) and 3-(3,3鈥?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路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路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路6H₂O and Ni(NO₃)₂路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.