An Unsymmetric Ligand Framework for Noncoupled Homo- and Heterobimetallic Complexes

Abstract

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, [Zn₂(PDIpCy)(THF)(OTf)₄] (1; THF = tetrahydrofuran and OTf = triflate), [Ni₂(PDIpCy)(THF)(OTf)₂](OTf)₂ (2), and [NiZn(PDIpCy)(THF)(OTf)₄] (3), are described. The one-electron-reduced compounds, [Zn₂(PDIpCy)(OTF)₃] (4), [Ni₂(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).