Photoactive Excited States in Explosive Fe(II) Tetrazine Complexes: A Time-Dependent Density Functional Theory Study

• Published in: Journal of physical chemistry. C 2016-12, Vol.120 (50), p.28762-28773
• Main Authors: Sifain, Andrew E, Bjorgaard, Josiah A, Myers, Thomas W, Veauthier, Jackie M, Chavez, David E, Prezhdo, Oleg V, Scharff, R. Jason, Tretiak, Sergei
• Format: Article
• Language: English
• Subjects: INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.6b10333

Time-dependent density functional theory was used to investigate optical absorption of novel Fe­(II) coordination complexes with tetrazine ligands. These octahedral compounds absorb near-infrared (NIR) light and can be applied as secondary explosives with low laser-initiation thresholds compared to penta­erythritol tetranitrate. Herein, numerous ligand architectures are studied to determine relationships between molecular structure and optical absorption in order to tune the low-energy charge transfer (CT) band. Geometrical structures and vertical excitation energies calculated with the TPSSh density functional and 6-311G basis set are in excellent agreement with experiment, with a maximum deviation from UV–vis spectra of 0.10 eV. By altering molecular substituents of the ligand scaffold, the CT band can be tuned between 500 and 1100 nm. Additional conjugation in the ligand scaffold pushes the CT band into the NIR region of the spectrum. Triazolo-tetrazine ligands shift the CT band by approximately 0.70 eV relative to that of Fe­(II) coordinated with bipyridine ligands. Oxygenated analogues of several compounds are also studied in order to predict optical response, while improving explosive performance. A natural population analysis suggests that the high nitrogen content of the ligand scaffolds in these energetic compounds lessens their metal-to-ligand charge transfer character compared to that of Fe­(II) coordinated with bipyridine ligands. The proposed model quantum chemistry is used to establish structure–property relationships for optical properties in this class of materials in order to make optical initiation with conventional lasers a more feasible approach.