Nowadays,
although research of proton conductive materials has
been extended from traditional sulfonated polymers to novel crystalline
solid materials such as MOFs, COFs, and HOFs, research on crystalline
ferrocene-based carboxylate materials is very limited. Herein, we
selected two hydrogen-bonded and π–π interactions-supported
ferrocenyl carboxylate frameworks (FCFs), [FcCO(CH2)2COOH] (FCF 1) and [FcCOOH] (FCF 2) (Fc = (η5-C5H5)Fe(η5-C5H4)) to fully investigate their water-mediated
proton conduction. Their excellent thermal, water, and chemical stabilities
were confirmed by the means of thermogravimetric analyses, PXRD, and
SEM determinations. The two FCFs indicate temperature- and humidity-dependent
proton conductive features. Intriguingly, their ultrahigh proton conductivities
are 1.17 × 10–1 and 1.01 × 10–2 S/cm, respectively, under 100 °C and 98% RH, which not only
are comparable to the commercial Nafion membranes but also rank among
the highest performing MOFs, HOFs, and COFs ever described. On the
basis of the structural analysis, calculated E
a value, H2O vapor adsorption, PXRD, and SEM measurements,
reasonable conduction mechanisms are highlighted. Our research provides
a novel inspiration for finding new high proton conducting crystalline
solid materials. Importantly, the outstanding conducting performance
of 1 and 2 suggests their, hopefully, potential
in fuel cells and related electrochemical fields.