350246-22-9Relevant academic research and scientific papers
Metallocorroles as sensing components for gas sensors: Remarkable affinity and selectivity of cobalt(III) corroles for CO vs. O2 and N 2
Barbe, Jean-Michel,Canard, Gabriel,Brandes, Stephane,Jerome, Francois,Dubois, Geraud,Guilard, Roger
, p. 1208 - 1214 (2004)
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/ P1/2 Co) 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.
Alkyl and aryl substituted corroles. 1. Synthesis and characterization of free base and cobalt containing derivatives. X-ray structure of (Me4Ph5Cor)Co(py)2
Guilard,Gros,Bolze,Jerome,Ou,Shao,Fischer,Weiss,Kadish
, p. 4845 - 4855 (2008/10/08)
The synthesis, spectroscopic properties, and electrochemistry of six different alkyl- and aryl-substituted Co(III) corroles are presented. The investigated compounds contain methyl, ethyl, phenyl, or substituted phenyl groups at the eight β-positions of the corrole macrocycle and four derivatives also contain a phenyl group at the 10-meso position of the macrocycle. Each cobalt corrole undergoes four reversible oxidations in CH2Cl2 containing 0.1 M tetra-n-butylammonium perchlorate and exists as a dimer in its singly and doubly oxidized forms. The difference in potential between the first two oxidations is associated with the degree of interaction between the two corrole units of the dimer and ranges from an upper value of 0.62 V, in the case of (Me6Et2Cor)Co, to a lower value of about 0.17 V, in the case of four compounds which have a phenyl group located at the 10-meso position of the macrocycle. These Co(III) corroles strongly coordinate two pyridine molecules or one carbon monoxide molecule in CH2Cl2 media, and ligand binding constants were evaluated using spectroscopic and electrochemical methods. The structure of (Me4Ph5Cor)Co(py)2 was also determined by X-ray diffraction. Crystal data: (Me4Ph5Cor)Co(py)2 ·3CH2Cl2·H2O, orthorhombic, a = 19.5690(4) A, b = 17.1070(6) A, c = 15.9160(6) A, V = 5328.2(5) A3, space group Pna21, Z = 2, 35 460 observations, R(F) = 0.069.
