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A novel one-dimensional (1D) oxalate-bridged coordination polymer of iron(III), {[NH(CH 3 )(C 2 H 5 ) 2 ][FeCl 2 (C 2 O 4 )]}  n  ( 1 ), exhibits remarkable humidity-sensing properties and very high proton conductivity at room temperature (2.70 × 10 -4 (Ω·cm) -1 at 298 K under 93% relative humidity), in addition to the independent antiferromagnetic spin chains of iron(III) ions bridged by oxalate groups ( J = -7.58(9) cm -1 ). Moreover, the time-dependent measurements show that 1 could maintain a stable proton conductivity for at least 12 h. Charge transport and magnetic properties were investigated by impedance spectroscopy and magnetization measurements, respectively. Compound 1 consists of infinite anionic zig-zag chains [FeCl 2 (C 2 O 4 )]  n  n   - and interposed diethylmethylammonium cations (C 2 H 5 ) 2 (CH 3 )NH + , which act as hydrogen bond donors toward carbonyl oxygen atoms. Extraordinarily, the studied coordination polymer exhibits two reversible phase transitions: from the high-temperature phase HT to the mid-temperature phase MT at T ~213 K and from the mid-temperature phase MT to the low-temperature phase LT at T ~120 K, as revealed by in situ powder and single-crystal X-ray diffraction. All three polymorphs show large linear thermal expansion coefficients.

materials

Humidity-Sensing Properties of an 1D Antiferromagnetic Oxalate-Bridged Coordination Polymer of Iron(III) and Its Temperature-Induced Structural Flexibility