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Perylenemonoimide (PMI)-carbazole (Cz) compact electron donor/acceptor dyads were prepared to study the relationship between the mutual orientation of the electron donor/acceptor in the dyads and the spin-orbit charge transfer intersystem crossing (SOCT-ISC) efficiency. The PMI and the Cz units are connected via either a C-C or C-N bond, or with an intervening phenyl moiety. The photophysical properties of the dyads were studied with steady state and time-resolved optical spectroscopies. The fluorescence of the PMI unit in the dyads was