Novel triplet germylenes in focus: normal vs. abnormal triplet exocyclic tetrazol-5-vinylidene germylenes at DFT

Substituent effects on stability (assumed as the singlet and triplet energy gaps, ΔΕ_S-T) of novel 1,4-disubstituted-tetrazole-5-vinylidene germylenes (normal, 1_R) and their corresponding 1,3-disubstituted-tetrazole-5-vinylidene germylenes (abnormal, 2_R) are computed and compared, at B3LYP/6-311++G** and M06/6-311++G**, where R = H, CN, CF₃, F, SH, C₆H₆, OMe, and OH. Interestingly, every triplet vinylidene germylene shows more stability than its corresponding singlet. Also, every triplet abnormal isomer (2_R) emerges to be more stable than its corresponding normal (1_R). All abnormal 2_R isomers show broader band gaps (ΔE_HOMO-LUMO) and higher nucleophilicity (N), but less electrophilicity (ω) than their corresponding normal 1_R isomers. The NICS (nuclear-independent chemical shift) results indicate that every 1_R (except singlet 2_Ph) emerges more aromatic than its corresponding 2_R. Our Hammet studies indicate that 1_R is more sensitive to the electronic effects of substituents, R, than 2_R. Electron-donating species increase N in both 1_R and 2_R, while electron-withdrawing groups increase stability.