Calculation of magnetic response properties of tetrazines

• Published in: RSC advances 2020-05, Vol.1 (31), p.18124-1813
• Main Authors: Orozco-Ic, Mesías, Celaya, Christian A, Sundholm, Dage
• Format: Article
• Language: English
• Subjects: Aromaticity; Benzene; Cartesian coordinates; Chemistry; Current density; Density functional theory; Derivatives; Magnetic fields; Magnetic properties; Magnetic shielding; Mathematical analysis; Molecular orbitals; Molecular structure
• ISSN: 2046-2069; 2046-2069
• DOI: 10.1039/d0ra01641a

Magnetic response properties of 1,2,3,5-tetrazine derivatives including the newly synthesized 4,6-diphenyl-1,2,3,5-tetrazine have been studied computationally at the density functional theory (DFT) level. Calculations of magnetically induced current densities and induced magnetic fields show that the unsubstituted 1,2,3,5-tetrazine is almost as aromatic as benzene. Separating the magnetic shielding functions into molecular orbital components provided additional insights into the magnetic response. The aromatic character estimated from magnetically induced current densities and induced magnetic fields shows that NICS π zz (0) values and ring-current strengths yield about the same degree of aromaticity, whereas NICS zz (0) and NICS zz (1) values are contaminated by σ electron contributions. The studied 1,2,3,5-tetrazine derivatives are less aromatic than the unsubstituted one. Calculations of magnetic response properties of 4,6-diphenyl-1,2,3,5-tetrazine showed that it is the least aromatic among the studied molecules according to the ring-current criterion, while 4,6-[1,2,3,5]-ditetrazinyl-1,2,3,5-tetrazine is as aromatic as 4,6-dimethyl-1,2,3,5-tetrazine and slightly less aromatic than the unsubstituted 1,2,3,5-tetrazine. Magnetic response properties of 1,2,3,5-tetrazine derivatives including the newly synthesized 4,6-diphenyl-1,2,3,5-tetrazine have been studied computationally at the density functional theory level.