C-13 CP MAS NMR-STUDIES OF TETRAAZAANNULENES - FAST PROTON-TRANSFER IN THE SOLID-STATE/

Full assignments of the high resolution C-13 CP/MAS solid state NMR sp ectra of a series of substituted dibenzotetraazaannulenes based on the parent macrocycle tetraazaannulene dagger (TAA) are reported. The exp ected number of resonances observed is compatible with the crystal str uctures in all cases, except that in the case of TAA only one resonanc e is observed in the region expected for C-8 and -15. This observation is interpreted as being a consequence of fast proton transfer in the solid-state coupled with rapid molecular rotation. Variable temperatur e studies of the maximum line broadening of the peaks indicates an act ivation energy of 8.4 kJ mol(-1). Methyl substituents on the ring lead to two peaks in the C=N/C-NH region; this is attributed to unequal po pulations of tautomers with no rotation of the molecule. The results a re compared to literature N-15 data. Variable temperature data on the methyl substituted systems are also consistent with the reported N-15 data, confirming that the tautomers are unequally populated.