Modulating electron transfer dynamics at hybrid interfaces via self-assembled multilayers

A method of preparing a self-assembled multilayer film on a substrate comprising a metal oxide surface region and a bulk region, the method comprising:

• contacting the metal oxide surface region with a bridging molecule having the general structure (L1)-(A)-(L2) to thereby form a covalently bonded self-assembled monolayer on the metal oxide surface region, wherein L1 and L2 are each independently a metal ion chelating moiety or a metal bonding moiety selected from the group consisting of —COOH, —PO3H2, —SO3H, —OPO3H, —OSO3H, —SiO3, —Ph(OH)2, —CH(CO2H)2, —CH═C(CN)CO2H, —CH═C(CO2H)2, —CONHOH, —CSSH, —CSOH, and any combination thereof, and A is a bridging moiety selected from the group consisting of alkyl, alkenyl, alkynyl, aromatic, heteroaromatic, heterocycloalkyl, cycloalkyl, and any combination thereof;
• contacting the self-assembled monolayer on the surface of the metal oxide surface region with a compound comprising a linking coordinating metal ion selected from the group consisting of Cu2+, Co2+, Ni2+, Zn2+, Mn3+, Fe2+, Sr2+, Al3+, V3+, In3+, Fe3+, Gd3+, Y3+, Yb3+, Nd3+, Ce3+, La3+, Sc3+, Dy3+, Zr4+, Ti4+, Sn4+, and any combination thereof, to thereby incorporate a coordinating metal into the self-assembled monolayer;
• and
• contacting the linking coordinating metal ion in the self-assembled monolayer with an active moiety selected from the group consisting of a chromophore, a catalyst, and an electroactive molecule bonded to the linking coordinating metal ion, to thereby bond the active moiety to the linking coordinating metal.