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We report the synthesis, crystal structures, and related properties of six new zeolite-like hexacyanometallates of formula unit T 3 (H 3 O) 2 [M(CN) 6 ] 2 ·uH 2 O (T = Co 2+ , Zn 2+ ; M = Ru II , Os II ). Their crystal structures were solved and refined from their X-ray powder diffraction patterns in combination with the IR and UV/Vis/NIR spectroscopic data. The Co and Zn ions are coordinated tetrahedrally to the N atoms of four CN groups. The deconvolution of the overlapped UV/Vis/NIR spectral bands provided conclusive evidence of the tetrahedral coordination of the Co atoms. These materials have porous frameworks, which are characterized by a 3D array of TN 4 tetrahedral units linked to the MC 6 octahedral blocks in a 3:2 ratio. From the IR spectroscopy results, we found that all of the compounds reported [a]

In this work, we report the synthesis and characterization of a bimetallic Prussian blue analogue containing Co and Mn as outer-sphere metals (CoMnHCF). The material was a solid solution and its characterization revealed a chemical composition of Co 2.05 Mn 0.95 [Fe(CN) 6 ] 2 · 12H 2 O. The electrochemistry of this novel material showed the existence of two redox waves displaying quasi-reversible kinetics, as expressed by the larger peak-to-peak separation upon increasing the potential sweep rate. Interestingly, the CoMnHCF solid exhibited high electrocatalytic activity for the oxidation of hydrogen peroxide, thus representing an appealing scaffold for the construction of biosensors. As a proof of concept, cholesterol oxidase was immobilized at the electrode surface by using a sol-gel method, and the cyclic voltammograms were recorded at increasing concentrations of cholesterol. The biosensor showed a detection limit of 30 μM and two linear ranges with excellent sensitivity of 385 mA cm À 2 M À 1 between 50 and 150 μM, and an adequate sensitivity of 80 mA cm À 2 M À 1 between 150 and 1 mM. To the best of our knowledge, this is the first biosensor application of a pre-synthesized bimetallic hexacyanometallate, thus exploiting its potential as an H 2 O 2 electrooxidation catalyst.

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