A Titration Method for Standardization of Aqueous Sodium Chlorite Solutions Using Thiourea Dioxide.

Accurate and cost-effective methods for the analysis of oxychlorine compounds in water are critical to modern chlorine-based water treatment. With alternatives to elemental chlorine and hypochlorite bleaches growing in popularity, simple quantification methods for the disinfectant chlorine dioxide (ClO2) in water, as well as chlorite (ClO2-) and chlorate (ClO3-), which are commonly used precursors in ClO2 generation, are required. However, currently, regulated standard methods require specialized equipment and do not effectively discriminate between molecular and ionic species. In this contribution, we present a simple titration-based method for chlorite determination in water using commercially available and easy-to-handle reagents. Specifically, chlorite is reduced with a slight excess of thioureadioxide (TUD). The remaining reductant is then back-titrated against a known amount of potassium permanganate, affording calculatable chlorite concentrations through measured consumption of a reductant and a clear visual endpoint upon accumulation of excess KMnO4. Straightforward methods for chlorite standardization with reasonable error and accuracy for field and/or lab application have the potential to greatly enhance quality assurance and therefore assist in resource deployment in water treatment.

Synthesis and Coordination Chemistry of a Benzannulated Bipyridine: 6,6'-Biphenanthridine.

The synthesis, characterization, and coordination chemistry of a doubly π-extended bipyridine analogue, 6,6'-biphenanthridine (biphe), is presented. The structure of the molecule has been determined in the solid state by X-ray diffraction, showing an angle of 72.6° between the phenanthridine planes. The free, uncoordinated organic molecule displays blue fluorescence in solution. It can be singly protonated with strong acids, and the protonated form displays more intense yellow emission. The effect of acid on the excited states is interpreted with the aid of TDDFT calculations. Two Ru(II) coordination complexes, tris(6,6'-biphenanthridine)ruthenium(II) dichloride, [Ru(biphe)3]Cl2, and bis(2,2'-bipyridine)(6,6'-biphenanthridine)ruthenium(II) tetraphenylborate, [Ru(bpy)2(biphe)](BPh4)2, are also reported and their structures determined in the solid state by X-ray diffraction. Both complexes display emission at 77 K that is strongly bathochromically shifted by almost 200 nm compared to that of the archetypal 3MLCT emitter [Ru(bpy)3]2+. Such a red shift is consistent with the more extended conjugation and lower-energy π* orbitals associated with the biphe ligand, lowering the energy of the 3MLCT excited state, as revealed by TDDFT calculations. The efficient non-radiative decay that is typical of such low-energy emitters renders the phosphorescence extremely weak and short-lived at ambient temperature, and rapid ligand photodissociation also competes with radiative decay, especially in the heteroleptic complex. Electrochemical analysis illustrates the effect of biphe's stabilized vacant π* manifold, with multiple reversible reductions evident at much less negative potentials than those observed for [Ru(bpy)3]2+.

The isolation, purification and complete characterization of the diterpene forskolin from nutritional supplements.

Forskolin (1) is a diterpene found in the Coleus forskohlii plant that has been examined for its medical properties resulting from adenylyl cyclase activation. This article describes a straightforward purification method of 1 from commercially available weight loss capsules. In addition, there has been some ambiguity with respect to the use of the name 'forskolin' to describe 1 and related diterpenes, which this report serves to eliminate. Herein we detail the complete spectroscopic characterization of purified 1 as well as its single crystal X-ray structure.

Zn-Templated synthesis of substituted (2,6-diimine)pyridine proligands and evaluation of their iron complexes as anolytes for flow battery applications.

Pseudo-octahedral iron complexes supported by tridentate N^N^N-binding, redox 'non-innocent' diiminepyridine (DIP) ligands exhibit multiple reversible ligand-based reductions that suggest the potential application of these complexes as anolytes in redox flow batteries (RFBs). When bearing aryl groups at the imine nitrogens, substitution at the 4-position can be used to tune these redox potentials and impact other properties relevant to RFB applications, such as solubility and stability over extended cycling. DIP ligands bearing electron-withdrawing groups (EWGs) in this position, however, can be challenging to isolate via typical condensation routes involving para-substituted anilines and 2,6-diacetylpyridine. In this work, we demonstrate a high-yielding Zn-templated synthesis of DIP ligands bearing strong EWGs. The synthesis and electrochemical characterization of iron(ii) complexes of these ligands is also described, along with properties relevant to their potential application as RFB anolytes.

Electrochemical hydrogenation of a benzannulated pyridine to a dihydropyridine in acidic solution.

The electrochemistry of pyridines in acidic solution is dominated by a 'weak acid' reduction on the cyclic voltammetry timescale. Here we show that electrochemical hydrogenation of a benzannulated pyridine, phenanthridine (1), to the biomimetic hydride donor 1,2-dihydrophenanthridine (1-H2) can occur selectively at glassy carbon electrodes over longer timescales of potentiostatic electrolysis.

Testing the Limits of the BOPHY Platform: Preparation, Characterization, and Theoretical Modeling of BOPHYs and Organometallic BOPHYs with Electron-Withdrawing Groups at ß-Pyrrolic and Bridging Positions.

Several BOPHY derivatives with and without ferrocene fragments, and with electron-withdrawing ester groups appended to the ß-pyrrolic positions have been prepared and characterized by NMR, UV/Vis near-infrared (NIR), high-resolution mass spectrometry, and fluorescence spectroscopy, as well as X-ray crystallography. The redox properties of new BOPHYs were probed by electrochemical (cyclic and differential pulse voltammetry) and spectroelectrochemical methods. In an attempt to prepare BOPHY derivatives with a cyano group at the bridging position using a similar approach for BODIPY cyanation, adducts from the nucleophilic attack of the cyanide anion on the bridging position in BOPHY have been isolated and characterized by spectroscopic methods. Oxidation of such adducts, however, resulted in formation of either the starting BOPHYs, or partial extrusion of the BF2 fragment from the BOPHY core, which was confirmed by spectroscopy and X-ray crystallography. DFT and TDDFT calculations on all target materials correlate well with the experimental data, and suggest the dramatic reduction of the nitrogen atom basicity at the hydrazine bridge of the BOPHY upon introduction of the cyano group at the bridging-carbon atom.