Exocyclic Coordination Complexes as Linkers

In the case of hole transfer from the AuP state, copper mediation is observed in the form of a hopping mechanism, even though no evidence for a Cu(II) intermediate was found. In the case of Ag(I), a super exchange-mediated mechanism is demonstrated and these systems offer an additional way to control and switch eT processes. In the case of electron transfer from ZnP to AuP+, the charge separated state lives for 10 to 40 ns, and its efficient generation (80% yield) competes with ZnP deactivation through ZnP, after a fast ( et = 5.1 x 10 s ) primary ET from ZnP to Cu(I)(phen)2, and a second ET process ( et = 1-5 x 10 s ) from Cu(I)(phen)2 to ZnP  

All of these examples show that the use of metal coordination at the periphery of the porphyrin chromophores can be extremely helpful in modular approaches targeting multiporphyrinic assemblies. As we will see later, the formation of coordination polymers has already found applications in the preparation of materials. 

---