title: Synthesis, spectroscopic and electrochemical studies of phosphoryl and carbomethoxyphenyl substituted corroles, and their anion detection properties.
abstract: The synthesis, electrochemical studies and anion detection properties of triphosphoryl () and triester corroles () are reported and compared with triphenylcorrole (). These corroles exhibited typical acid-base binding behaviour in CH3CN and were converted to monoprotonated and dianionic species, respectively. has shown a ∼30 fold lower Keq value for monoprotonation than that of in a TFA-CH3CN medium. The detection ability of these corroles was also tested in acetonitrile towards various anions. The observed spectral changes in free-base corroles () are due to anion-induced deprotonation rather than the hydrogen bonding interaction between the imino protons of the corrole moiety with anions. and have shown higher equilibrium constants with F(-) ions (4.7 × 10(3) fold higher for and 9.7 × 10(3) fold higher for ) as compared to and are able to detect 0.06 μM of F(-) ions. The Cu(iii) and Ag(iii) complexes of and exhibited an anodic shift of ∼250 mV in first ring oxidation and ∼100-150 mV in metal centred reduction as compared to the Cu(iii) and Ag(iii) complexes of . The anodic shift in the redox potentials, lower protonation constants and lower detection limit of anions have been explained in terms of the electron-withdrawing nature of the diethylphosphite and carbomethoxy substituents at the meso-phenyl positions of the corrole ring.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee - 247667, India. sankafcy@iitr.ac.in.
authors.forename: Pinky
authors.initials: P
authors.lastname: Yadav
authors.forename: Muniappan
authors.initials: M
authors.lastname: Sankar
mesh_terms: D000838:Anions / Q000032:analysis / Q000737:chemistry*; D056831:Coordination Complexes / Q000138:chemical synthesis* / Q000737:chemistry; D003300:Copper / Q000737:chemistry; D004563:Electrochemistry; D008665:Metalloporphyrins / Q000737:chemistry*; D015394:Molecular Structure; D011166:Porphyrins / Q000737:chemistry*; D012834:Silver / Q000737:chemistry; D013057:Spectrum Analysis
chemical_list: D000838:Anions; D056831:Coordination Complexes; D008665:Metalloporphyrins; D011166:Porphyrins; C431863:corrole; D012834:Silver; D003300:Copper