An Unsymmetric Ligand Framework for Noncoupled Homo- and Heterobimetallic Complexes

Ruth M Haas; Zachary Hern; Stephen Sproules; Corinna R Hess

doi:10.1021/acs.inorgchem.7b02294

An Unsymmetric Ligand Framework for Noncoupled Homo- and Heterobimetallic Complexes

Inorg Chem. 2017 Dec 18;56(24):14738-14742. doi: 10.1021/acs.inorgchem.7b02294. Epub 2017 Nov 27.

Authors

Ruth M Haas¹, Zachary Hern², Stephen Sproules³, Corinna R Hess¹

Affiliations

¹ Department of Chemistry and Catalysis Research Center, Technische Universität München , Lichtenbergstraße 4, Garching 85748, Germany.
² Department of Chemistry, University of Texas at San Antonio , San Antonio, Texas 78249, United States.
³ School of Chemistry, University of Glasgow , University Avenue, Glasgow G12 8QQ, U.K.

PMID: 29172466
DOI: 10.1021/acs.inorgchem.7b02294

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).