Fig. 2a 
Experimental time-of-flight spectra of NO+ (m/q = 30) for different time delays between pump and probe pulses in the case of p-NA.

Fig. 2b 
Normalized differential mass spectra of NO+ for p-NA vs. pump-probe time delay obtained by performing the difference between the spectra acquired with and without the probe pulse.

Fib. 2c
NO+ yield in the case of p-NA obtained by integrating the time-of-flight spectra of the high-energy NO+ ion emitted in the forward direction in a 3-eV kinetic energy window centred on the maximum of the corresponding shoulder. 
Fitting curve with an exponential rise time of 9.3 fs and an exponential relaxation time of 22.4 fs.
Impulsive response function. 

Fig. 2d
NO+ yield in the case of p-NA, m-NA and nd-NA obtained by integrating the time-of-flight spectra of the high-energy NO+ ion emitted in the forward direction.

Fig. 3a-c-d 
a) Calculated temporal evolution of the average Root Mean Square Deviation (RMSD) of all the trajectories initialized in electronic state D6 of p-NA with respect to the planar minimum geometry. The lower the values of the RMSD the closer to the planar geometry. 
c) Temporal evolution of the average charge in the ELF basins for the lone pair of N in the NH2 group and the C-N bond connecting it to the ring. 
d) Temporal evolution of the average kinetic energy of the nuclear wave packet and the average Dyson norm corresponding to the orbital that results from the projection of the whole wave packet in the mono-cation at each time-step of the surface hopping trajectory onto the dication. 

Fig. 3b Blue Map
Snapshots of the evolution of the electronic density (bemzene ring). 

Fig. 3b Green Map
Snapshots of the evolution of the electronic density (C-N bond). 

Fig. 3b Red Map
Snapshots of the evolution of the electronic density (lone pair of the N).  

Fig. 4a
Temporal evolution of the energy difference between the D1, D2 and D6 states of the cation and ground state of the dication for all the p-NA trajectories (obtained using he script README_dataAnalysisFort-spectra_Fig4a)

Fig. 4b
Normalized number of trajectories requiring 5, 6, 7 and 8 VIS-NIR photons to reach the ground state S0 of the dication in p-NA, for the trajectories initiated in the highest electronic states (D6). 

Fig. 4c-e
Normalized number of trajectories requiring the absorption of 6 VIS-NIR photons to reach S0 compared with the measured yields for p-NA, m-NA and nd-NA, respectively, obtained by integrating the time-of-flight spectra of the high-energy NO+ ion emitted in the forward direction. Fits to the experimental spectra.
 
Extended Data Fig. 1: PEPICO measurements.
PEPICO matrix for p-NA. The x-axis represents the binding energy (BE), the y-axis the mass to charge ratio (m/q) and the z-axis the number of events collected at the detector normalized to the maximum number of events. 

Extended Data Fig. 2: C–N and C–C bond lengths for p-NA
Variation of the C–N and C–C bond lengths for p-NA, m-NA and nd-NA. The dynamics was started from the D6 state of p-NA, D8 state of m-NA and D5 state from nd-NA.

Extended Data Fig. 3: Evolution of the electronic density in the NO2 region.
Temporal evolution of the average charge in the ELF basins for the N–O bonds group and the C–N bond connecting it to the ring.

Extended Data Fig. 4: Population of adiabatic states.
Time evolution of the population of all adiabatic states included in the SH calculations initiated in the D6 state of p-NA.

Extended Data Fig. 5: Coulomb Explosion.
Zoom of PEPICO measurements around m/q=30 (NO+) for the three investigated molecules. T

Extended Data Fig. 6: Mass spectra produced by attosecond excitation.
Mass spectra around fragment NO+ (m/q=30) measured by using the attosecond beamline after XUV excitation.

Extended Data Fig. 7: PEPIPICO measurements in p-NA.
Ion-ion coincidence map within the time-of-flight range where correlations between ion pairs with m/q =30 and m/q =108 and between ion pairs with m/q =46 and m/q =92 are expected.