1H-NMR spectra of DBH (1), DBO (2) and of the synthetic precursor to1, 1,4-phenyl-2,4,6-triazatricyclo[5.2.1.02,6]heplanc-3,5-dione (3), were recorded in acetone-d6and C6D6at 500 MHz. Assignment was aided by complete resolution of signals of1and3in C6D6by aromatic solvent-induced shifts (ASIS). The effect of the change from phenyllriazolinedione to a diazene functional group on the chemical shifts of theexo,endoandsyn,antiprotons was investigated. The chemical shifts of theexo,endoprotons of1are exceptionally sensitive to the functional group at the hetero substituted bridge in the DBH skeleton. However, the relative chemical shift of thesyn,antiproton pair is independent of the nature of the functional group. The role of stereochemical effects on these chemical shifts is discussed.