Zero-Field Splitting of the Electronic Ground and Lowest Excited Triplet States of 2,2-Dinaphthylcarbene in n-Hexane at 1.7 K

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Abstract

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 T0 and excited T1 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 T0 state. The analysis provided direct information about the ZFS parameters of the T0 and T1 states: E0 = 0.022 ± 0.001 cm-1, D0 = 0.477 ± 0.001 cm-1, E1 = 0.006 ± 0.0002 cm-1, and D1 = 0.043 ± 0.0005 cm-1.

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