New light from an old reagent: chemiluminescence from the reaction of potassium permanganate with sodium borohydride

When aqueous sodium borohydride (50 mM) is added to a solution of potassium permanganate (1mM, in sodium hexametaphosphate) at acidic pH, bright red-orange emission is easily visible in a darkened room. This chemiluminescence emission is due to an excited state of manganese (II) that undergoes solution phase phosphorescence and provides an excellent opportunity for students to explore the relationship between the initial oxidation state of the manganese and the likelihood of luminescence. Not surprisingly Mn(VII), Mn(IV) and Mn(III) all give rise to chemiluminescence where as Mn(II) fails to react.

Fluorescent photoinduced electron transfer (PET) sensors for anions; from design to potential application

This mini review highlights the synthesis and photophysical evaluation of anion sensors, for nonaqueous solutions, that have been developed in our laboratories over the last few years. We have focused our research mainly on developing fluorescent photoinduced electron transfer (PET) sensors based on the fluorophore-spacer-anion receptor principle using several anthracene (emitting in the blue) and 1,8-naphthalimide (emitting in the green) fluorophores, with the aim of targeting biologically and industrially relevant anions such as acetates, phosphate and amino acids, as well as halides such as fluoride. The receptors and the fluorophore are separated by a short methyl or ethyl spacer, where the charge neutral anion receptors are either aliphatic or aromatic urea (or thiourea) moieties. For these, the anion recognition is through hydrogen bonding, yielding anion:receptor complexes. Such bonding gives rise to enhanced reduction potential in the receptor moieties which causes enhancement in the rate of PET quenching of the fluorophore excited state from the anion:receptor moiety. This design can be further elaborated on by incorporating either two fluorophores, or urea/thiourea receptors into the sensor structures, using anthracene as a fluorophore. For the latter design, the sensors were designed to achieve sensing of bis-anions, such as di-carboxylates or pyrophosphate, where the anion bridged the anthracene moiety. In the case of the naphthalimide based mono-receptor based PET sensors, it was discovered that in DMSO the sensors were also susceptible to deprotonation by anions such as F− at high concentrations. This led to substantial changes in the absorption spectra of these sensors, where the solution changed colour from yellow/green to deep blue, which was clearly visible to the naked eye. Hence, some of the examples presented can act as dual fluorescent-colorimetric sensors for anions. Further investigations into this phenomenon led to the development of simple colorimetric sensors for fluorides, which upon exposure to air, were shown to fix carbon dioxide as bicarbonate.

Simultaneous control of spectroscopic and electrochemical properties in functionalised electrochemiluminescent tris(2,2'-bipyridine)ruthenium(II) complexes

Using a combination of electrochemical, spectroscopic and computational techniques, we have explored the fundamental properties of a series of ruthenium diimine complexes designed for coupling with other molecules or surfaces for electrochemiluminescence (ECL) sensing applications. With appropriate choice of ligand functionality, it is possible to manipulate emission wavelengths while keeping the redox ability of the complex relatively constant. DFT calculations show that in the case of electron withdrawing substituents such as ester or amide, the excited state is located on the substituted bipyridine ligand whereas in the case of alkyl functionality it is localised on a bipyridine. The factors that dictate annihilation ECL efficiency are interrelated. For example, the same factors that determine ΔG for the annihilation reaction (i.e. the relative energies of the HOMO and LUMO) have a corresponding effect on the energy of the excited state product. As a result, most of the complexes populate the excited state with an efficiency (Φex) of close to 80% despite the relatively wide range of emission maxima. The quantum yield of emission (Φp) and the possibility of competing side reactions are found to be the main determinants of ECL intensity.

Annihilation electrogenerated chemiluminescence of mixed metal chelates in solution : Modulating emission colour by manipulating the energetics

We demonstrate the mixed annihilation electrogenerated chemiluminescence of tris(2,2′-bipyridine)ruthenium(ii) with various cyclometalated iridium(iii) chelates. Compared to mixed ECL systems comprising organic luminophores, the absence of T-route pathways enables effective predictions of the observed ECL based on simple estimations of the exergonicity of the reactions leading to excited state production. Moreover, the multiple, closely spaced reductions and oxidations of the metal chelates provide the ability to finely tune the energetics and therefore the observed emission colour. Distinct emissions from multiple luminophores in the same solution are observed in numerous systems. The relative intensity of these emissions and the overall emission colour are dependent on the particular oxidized and reduced species selected by the applied electrochemical potentials. Finally, these studies offer insights into the importance of electronic factors in the question of whether the reduced or oxidized partner becomes excited in annihilation ECL. This journal is

New perspectives on the annihilation electrogenerated chemiluminescence of mixed metal complexes in solution

Preliminary explorations of the annihilation electrogenerated chemiluminescence (ECL) of mixed metal complexes have revealed opportunities to enhance emission intensities and control the relative intensities from multiple luminophores through the applied potentials. However, the mechanisms of these systems are only poorly understood. Herein, we present a comprehensive characterisation of the annihilation ECL of mixtures of tris(2,2′-bipyridine)ruthenium(ii) hexafluorophosphate ([Ru(bpy)3](PF6)2) and fac-tris(2-phenylpyridine)iridium(iii) ([Ir(ppy)3]). This includes a detailed investigation of the change in emission intensity from each luminophore as a function of both the applied electrochemical potentials and the relative concentrations of the two complexes, and a direct comparison with two mixed (Ru/Ir) ECL systems for which emission from only the ruthenium-complex was previously reported. Concomitant emission from both luminophores was observed in all three systems, but only when: (1) the applied potentials were sufficient to generate the intermediates required to form the electronically excited state of both complexes; and (2) the concentration of the iridium complex (relative to the ruthenium complex) was sufficient to overcome quenching processes. Both enhancement and quenching of the ECL of the ruthenium complex was observed, depending on the experimental conditions. The observations were rationalised through several complementary mechanisms, including resonance energy transfer and various energetically favourable electron-transfer pathways.