“…Notably, the split appearances of ν CN,antisym and ν CN,sym modes appear to be a sensitive measure for the changes in the molecular geometry, including the symmetry with the dicyanomethylene group. 18,82,83 The very weak ν CN,sym mode of DCM appearing only in the S 1 /CT spectrum also supports the symmetry changes with the ICT, where the twisted dimethylamino group of DCM may result in much more minor changes in the molecular symmetry compared to the twisted julolidine group of LD688. Gaffney and co-workers investigated the ICT dynamics of 9-(2,2-dicyanovinyl)julolidine by time-resolved infrared spectroscopy, where the excited-state infrared modes of ν CN,antisym and ν CN,sym were observed at 2115 and 2155 cm −1 , respectively.…”