Dalton Transactions

Metallocorroles as sensing components for gas sensors: Remarkable affinity and selectivity of cobalt(III) corroles for CO vs. O2 and N 2

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Most commercially available CO detectors are based upon metal oxides or electrochemical cell technologies. None of these approaches use the selective adsorption of CO gas on a molecular complex. Conversely, cobalt(III) corroles can bind small gaseous molecules allowing them for an application as sensing components for gas detectors. Here we describe the ability of cobalt corroies to selectively coordinate carbon monoxide vs. dinitrogen and dioxygen. The coordination properties were determined in the solid state and the adsorption characteristics were compared to those of the reference compound (To-PivPP)Fe(1,2-Me2Im), known for its remarkable CO binding properties. The adsorption data evidence that the selectivity, affinity and capacity of the cobalt(III) corroies for CO are larger than those of the porphyrin complex. However, from a chemical point of view, the selectivity of cobalt(III) corroies for CO vs. O2 is infinite since these derivatives do not bind O2 while (To-PivPP)Fe(1,2-Me2Im) does with an M value (P1/2O2/ P1/2Co) equal to 51. In this manuscript we also show that the affinity of cobalt(III) corroies for CO is closely related to the Lewis acid character of the central cobalt(III) ion and therefore to the nature of the substituents at the periphery of the corrole macroring.