The invention provides systems having an electron transfer moiety tethered to an electrode by a conductive spacer moiety. A biasing potential applied to the electrode reduces the electron transfer moiety to form a reduced electron transfer species capable of absorbing a photon, to form an excited electron transfer species. An electron accepting moiety accepts an electron from the excited electron transfer species, to form a reduced electron acceptor. The reduced electron acceptor may for example be used in hydrogen generation reactions.