New A2B-type-(Mn+)-corrolate compounds (3 structural studies) that include the oxo(5,15-bis(pentafluorophenyl)-10-(R)corrolatochromium(V) [R = 2- / 3-thienyl (1a / 2a), 3-thianaphthyl (3a)] species are reported. The first examples of meso-A2(thienyl) and Cr-A2B-corrole types are represented herein. Charac-terization includes CV, EPR, 2-D (1H, 13C) NMR and UV-Vis spectroscopy, mass-spectrometry and elemental analysis. Compounds 1a-3a have enabled analyte binding capacity studies. [Cu2+???(O)Cr(cor)] binding repre-sents a new selective mode of corrole-based detection, whereas free-base A2B-corroles exhibited limited Mn+-selectivity. The 10-position substitution affects optical profiles in analyte titrations. A limited amount of PPh3 O-atom uptake from the [(O)Cr(cor)] was also demonstrated.
Various R/Ar?functionalized Sn(5,10,15?tris(pentafluorophenyl)corrolate) derivatives are reported herein including the first Fc?Sn?corrolate species. The isopropyl?, sec?butyl?, 2?methyl?n?butyl?, phenyl?, 2?thienyl?, ferrocenyl?tin species have been prepared and characterized through 1H?, 13C?, 119Sn?, and HMQC?NMR spectroscopy, mass spectrometry, UV?vis spectroscopy, photoluminescent spectroscopy, and cyclic voltammetry studies. JC/H?Sn NMR spectroscopic couplings and ring?current effects (upfield shifting) were determined for the R?Sn axial protons and carbons. Such NMR spectroscopic aspects are discussed for these model systems. Compound Sn?Ph bond cleavage was achieved by treatment with I2.
A novel rechargeable meso-aryl Bodipy?based Cys sensing ensemble has been developed (“turn on,” ΦF = <0.05 ? 0.72, limit of detection = 6.0 × 10?6 M) with exceptional selectivity over homocysteine, N?acetylcysteine, glutathione (GSH) and methionine.
New reversible Bodipy?based zinc (II) ensemble for selective “turn?on” fluorescence sensing of ATP and PPi in aqueous media was developed. The sensing mode involves demetallation of the weakly fluorescent 1?Zn2+ by ATP and PPi, leading to fluorescence enhancement due to production of fluorescent 1. The interaction between probe and analyte was studied by different techniques, such as NMR, HRMS and fluorometric titration. The detection limits were estimated on μM range (2.4 μM for ATP and 1.0 μM for PPi), which is much lower than that in biological samples. The probe is reversible; after interaction with PPi or ATP, 1?Zn2+ can be recharged again by the addition of Zn2+. Moreover, Bodipy itself shows selectivity to Zn2+, and Bodipy?Zn2+ ensemble formation is possible in the presence of other interfering metal ions.
Highly specific and sensitive fluorescence detection for hypochlorite in nonbiotic pure water (rapid “turn?on”, ~400 fold, λem ~560 nm) as well as in living neuronal cell cultures (neutral pH) involves oxidation of a 2?sulfide?2?benzoic acid pendent group in a new meso?thienyl?Bodipy Donor?Acceptor probe.