Supramolecular ferrocene-fullerene constructs in which the donor, ferrocene linked to a benzo-18-crown-6entity (Fc-crown), was self-assembled with the acceptor, fullerene bearing one or two alkyl ammonium ions(NH
3+-C
60), yielding dyads or a triad, respectively. The newly formed conjugates were characterized byspectroscopic (fluorescence, electospray ionization-mass, and
1H NMR) and electrochemical methods. Theadopted crown ether-alkyl ammonium ion binding strategy resulting in stable donor-acceptor conjugateswas also supported by the computational studies performed at the DFT B3LYP/3-21G(*) level in addition tothe binding constants obtained from fluorescence quenching studies. The experimentally calculated free-energy changes indicated exothermic light-induced charge-separation process. Accordingly, efficient photoinduced charge-separation processes were confirmed by the combination of the time-resolved fluorescenceand nanosecond transient absorption spectral measurements. The rates of charge recombination were foundto be 2-3 orders of magnitude lower, yielding radical ion-pairs, Fc
+-crown/NH
3+-C
60- with lifetimes in the10-240 ns range. Generally, by increasing the donor-acceptor distance, a decrease in both
kCS and
kCR wasobserved for the supramolecular ferrocene-fullerene dyads; that is, the lifetimes of Fc
+-crown/NH
3+-C
60-changed from 10 to 165 ns. However, for the triad, involving two ferrocene donors of varying donor-acceptor distances, the
kCR originating from the far-side located ferrocene was found to be 240 ns while the
kCR from the near-side located ferrocene was faster than the time duration of the nanosecond laser pulse (6ns).