ja5b10999_si_003.cif (5.76 kB)
Three-Dimensional Metal-Catecholate Frameworks and Their Ultrahigh Proton Conductivity
dataset
posted on 2015-12-16, 00:00 authored by Nhung
T. T. Nguyen, Hiroyasu Furukawa, Felipe Gándara, Christopher A. Trickett, Hyung Mo Jeong, Kyle E. Cordova, Omar M. YaghiA series
of three-dimensional (3D) extended metal catecholates
(M-CATs) was synthesized by combining the appropriate metal salt and
the hexatopic catecholate linker, H6THO (THO6– = triphenylene-2,3,6,7,10,11-hexakis(olate)) to give Fe(THO)·Fe(SO4) (DMA)3, Fe-CAT-5, Ti(THO)·(DMA)2, Ti-CAT-5, and V(THO)·(DMA)2, V-CAT-5 (where DMA
= dimethylammonium). Their structures are based on the srs topology and are either a 2-fold interpenetrated (Fe-CAT-5 and Ti-CAT-5)
or noninterpenetrated (V-CAT-5) porous anionic framework. These examples
are among the first catecholate-based 3D frameworks. The single crystal
X-ray diffraction structure of the Fe-CAT-5 shows bound sulfate ligands
with DMA guests residing in the pores as counterions, and thus ideally
suited for proton conductivity. Accordingly, Fe-CAT-5 exhibits ultrahigh
proton conductivity (5.0 × 10–2 S cm–1) at 98% relative humidity (RH) and 25 °C. The coexistence of
sulfate and DMA ions within the pores play an important role in proton
conductivity as also evidenced by the lower conductivity values found
for Ti-CAT-5 (8.2 × 10–4 S cm–1 at 98% RH and 25 °C), whose structure only contained DMA guests.
