Understanding the comparative oxidative abilities of high-valent metal-oxo/hydroxo/hydroperoxo species holds the key to robust biomimic catalysts that perform desired organic transformations with very high selectivity and efficiency. The comparative oxidative abilities of popular high-valent iron-oxo and manganese-oxo species are often counterintuitive, for example, oxygen atom transfer (OAT) reaction by [(Me2EBC)­MnIV–OOH]3+, [(Me2EBC)­MnIV–OH]3+, and [(Me2EBC)­MnIVO]2+ (Me2EBC = 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]­hexadecane) shows extremely high reactivity for MnIV–OOH species and no reactivity for MnIV–OH and MnIVO species toward alkyl/aromatic sulfides. Using a combination of density functional theory (DFT) and ab initio domain-based local pair natural orbital coupled-cluster with single, double, and perturbative triples excitation (DLPNO-CCSD­(T)) and complete-active space self-consistent field/N-electron valence perturbation theory second order (CASSCF/NEVPT2) calculations, here, we have explored the electronic structures and sulfoxidation mechanism of these species. Our calculations unveil that MnIV–OOH reacts through distal oxygen atom with the substrate via electron transfer (ET) mechanism with a very small kinetic barrier (16.5 kJ/mol), placing this species at the top among the best-known catalysts for such transformations. The MnIV–OH and MnIVO species have a much larger barrier. The mechanism has also been found to switch from ET in the former to concerted in the latter, rendering both unreactive under the tested experimental conditions. Intrinsic differences in the electronic structures, such as the presence and absence of the multiconfigurational character coupled with the steric effects, are responsible for such variations observed. This comparative oxidative ability that runs contrary to the popular iron-oxo/hydroperoxo reactivity will have larger mechanistic implications in understanding the reactivity of biomimic catalysts and the underlying mechanisms in PSII.

A simple fluorescent sensor of zinc-terpyridine complex of the terpyridine ligand 4'-(3,4,5-trimethoxyphenyl)-2,2' : 6',2''-terpyridine was prepared and utilized for selective sensing of pyrophosphate anion (PPi) in aqueous medium at physiological pH. The sensor complex showed an excellent selectivity of PPi over various other anions such as Cl À , F À , Br À , I À , CO 3 2À , HCO 3 À , NO 3 À , OH À , HPO 4 2À , SO 4 2À , SO 3 2À , S 2 O 3 2À in water. UV-Visible and fluorescence spectroscopic method have been used to perform the detection study. The sensor complex showed~50 fold enhancement of fluorescence intensity upon addition of PPi and excellent sensitivity with lowest limit of detection (LOD) for the detection of PPi anion was found to be~300 nM.