Two-step insertion/release of electrolytic cations in redox-active hydrogen-bonding nanoporous coordination crystals

Abstract

Solid-state cyclic voltammetry (CV) of redox-active H-bonding {[Ru^III(Hbim)₃]}_n (1) 1-D nanoporous crystals was performed using single crystals in MeCN solutions containing seven electrolyte cations with different effective ionic radii (EIRs). Two cations must be included to every nanochannel unit in {[Ru^IIRu^II]²⁻} reductive states by a two-step and multi-electron transfer reaction through the {[Ru^IIIRu^II]⁻} mixed-valency state. This study is the first to use solid-state CV to determine the EIR limitation of cations confinable in these crystals.