Results of optical studies of a new single-molecule system, terrylene molecules in a 2,3-dichloronaphthalene crystal, are presented for the rst time. Analysis of the second-order uorescence intensity correlation function shows that the external heavy-atom eect (due to the chlorine atoms) contributes to the increase of the intersystem crossing rate constant for the S1 → T1 transition, by one order of magnitude, whereas the rate constant for the T1 → S0 transition is only weakly inuenced.