We introduce a new unsymmetric ligand, PDIpCy (PDI = pyridyldiimine; Cy = cyclam), that offers two distinct, noncoupled coordination sites. A series of homo- and heterobimetallic complexes, [Zn-2(PDIpCy)(THF)(OTf)(4)](1; THE = tetrahydrofuran and OTf =triflate), [Ni-2(PDIpCy)(THF)(OTf)(2)] (OTf)(2) (2), and [NiZn(PDIpCy)(THF)(OTf)(4)] (3), are described. The one-electron-reduced compounds, [Zn-2(PDIpCy)(OTF)(3)] (4), [Ni-2(PDIpCy)(OTf)](OTf)(2) (5), and [NiZn(PDIpCy)(OTf)(3)] (6), were isolated, and their electronic structures were characterized. The reduced compounds are charge-separated species, with electron storage at either the PDI ligand (4) or at the PDI-bound metal ion (5 and 6).