Journal of Physical Chemistry A, Vol.103, No.17, 3155-3162, 1999
Zero-field splitting of the electronic ground and lowest excited triplet states of 2,2-dinaphthylcarbene in n-hexane at 1.7 K
The triplet-triplet fluorescence spectra of a new carbene, 2,2-dinaphthylcarbene in n-hexane and n-heptane, were studied at cryogenic temperatures. Synthesis of the carbene precursor, 2,2-dinaphthyldiazomethane, is described. Spectral holes were burned within the inhomogeneous 0,0 fluorescence excitation line assigned to the pseudo-E/trans conformer. The complicated pattern of burned holes was interpreted with a model taking into account the zero-field splitting (ZFS) of the ground T-0 and excited T-1 triplet states and the selectivity of the intersystem crossing channel. The unusual observation of antiholes was attributed to the extremely long spin-lattice relaxation time in the T-0 state. The analysis provided direct information about the ZFS parameters of the To and Ti states: E-0 = 0.022 +/- 0.001 cm(-1), D-0 = 0.477 +/- 0.001 cm(-1), E-1 = 0.006 +/- 0.0002 cm(-1) and D-1 = 0.043 +/- 0.0005 cm(-1).