On
the basis of the concept that the design of a mixed valence
system is a key route to create electronic conducting frameworks,
we propose a unique idea to rationally produce mixed valency in an
ionic donor/acceptor chain (i.e., D+A– chain). The doping of a redox-inert (insulator) dopant (P) into
a D+A– chain in place of neutral D enables
the creation of mixed valency A0/A– domains
between P units: P–(D+A–)nA0–P, where n is directly dependent on the dopant ratio, and charge transfer through
the P units leads to electron transport along the framework. This
hypothesis was experimentally demonstrated in an ionic DA chain synthesized
from a redox-active paddlewheel [Ru2II,II] complex
and TCNQ derivative by doping with a redox-inert [Rh2II,II] complex.