Ionicity Diagrams for Electron-Donor and -Acceptor Metal-Organic Frameworks: DA Chains and D2A Layers Obtained from Paddlewheel-Type Diruthenium(II,II) Complexes and Polycyano-Organic Acceptors.

Recent developments in research concerning metal-organic frameworks and coordination polymers have provided the successful design of charge-variable molecular frameworks. However, few comprehensive studies exist that investigate the control of charge states in series of molecular frameworks such as these. Herein, we discuss the ionicity diagrams of two series containing electron-donor (D) and -acceptor (A) units: one-dimensional DA chains and two-dimensional D2A layers. The series were obtained by reacting paddlewheel-type diruthenium(II,II) complexes ([Ru2II,II]), which served as D units, with the polycyano-organic acceptors N,N'-dicyanoquinodiimine (DCNQI) and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ), which served as A units. Fifteen novel members of neutral charged DA chains were fabricated in this study to characterize the ionicity diagrams for DA and D2A systems.