The fluorescence spectrum of crystals grown from newly synthesized 4-(dimethylamino)benzonitrile (DMABN), measured from 25 down to -112 degreesC, consists of a single emission band originating from a locally excited (LE) state. The fluorescence decay of the DMABN crystals is single exponential at all temperatures investigated. These results show that intramolecular charge transfer (ICT) does not occur in crystalline DMABN. The additional red-shifted emission bands and multiexponential fluorescence decays previously reported for DMABN crystals are attributed to a minor amount of the impurity 4-(dimethylamino)benzaldehyde, the synthetic precursor of commercial DMABN. (C) 2003 Elsevier B.V. All rights reserved.