In electrogenerated chemiluminescence, also known as electrochemiluminescence (ECL), electrochemically generated intermediates undergo a highly exergonic reaction to produce an electronically excited state that then emits light. These electron-transfer reactions are sufficiently exergonic to allow the excited states of luminophores, including polycyclic aromatic hydrocarbons and metal complexes, to be created without photoexcitation. For example, oxidation of [Ru(bpy)(3)](2+) in the presence of tripropylamine results in light emission that is analogous to the emission produced by photoexcitation. This review highlights some of the most exciting recent developments in this field, including novel ECL-generating transition metal complexes, especially ruthenium and osmium polypyridine systems; ECL-generating monolayers and thin films; the use of nanomaterials; and analytical, especially clinical, applications.

Two novel polyarginine labelled ruthenium polypyridyl dyes are reported, one conjugated to five, (Ru-Ahx-R 5 ), and one to eight arginine residues, (Ru-Ahx-R 8 ).Both complexes exhibit long-lived, intense, and oxygen sensitive luminescence. Luminescent dye molecules capable of passive cell delivery may be used as molecular probes for example in cellular imaging, cell biology, molecular biology, microbiology, and flow cytometry applications.The majority of probes used in cellular imaging are fluorescent and based on organic, typically polyaromatic, chromophores. The short luminescence lifetimes of such species, typically <10 ns, limits their environmental sensitivity, e.g., towards molecular oxygen, and their application for fluorescent lifetime imaging (FLIM).

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A novel mitochondrial localizing ruthenium(II) peptide conjugate capable of monitoring dynamic changes in local O2 concentrations within living cells is presented. The complex is comprised of luminescent dinuclear ruthenium(II) polypyridyl complex bridged across a single mitochondrial penetrating peptide, FrFKFrFK-CONH2 (r = D-arginine). The membrane permeability and selective uptake of the peptide conjugate at the mitochondria of mammalian cells was demonstrated using confocal microscopy. Dye co-localization studies confirmed very precise localization and preconcentration of the probe at the mitochondria. This precision permitted collection of luminescent lifetime images of the probe, without the need for co-localizing dye and permitted semiquantitative determination of oxygen concentration at the mitochondria using calibration curves collected at 37 °C for the peptide conjugate in PBS buffer. Using Antimycin A the ability of the probe to respond dynamically to changing O2 concentrations within live HeLa cells was demonstrated. Furthermore, based on lifetime data it was evident that the probe also responds to elevated reactive oxygen species (ROS) levels within the mitochondria, where the greater quenching capacity of these species led to luminescent lifetimes of the probe at longer Antimycin A incubation times which lay outside of the O2 concentration range. Although both the dinuclear complex and a mononuclear analogue conjugated to an octaarginine peptide sequence exhibited some cytotoxicity over 24 h, cells were tolerant of the probes over periods of 4 to 6 h which facilitated imaging. These metal-peptide conjugated probes offer a valuable opportunity for following dynamic changes to mitochondrial function which should be of use across domains in which the metabolic activity of live cells are of interest from molecular biology and drug discovery.

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Mind the gap: A complete, cooperative spin transition for a mononuclear Mn(III) complex is reported with an 8 K hysteresis window. Raman spectra collected at a single temperature in warming and cooling modes confirm the electronic bistability within the hysteresis loop. The source of the cooperativity is a disconnection in the hydrogen-bonded 1D chains that connect adjacent cations owing to an order-disorder transition in the PF(6)(-) counterion.

A mononuclear ruthenium(II) polypyridyl complex with an enlarged terpyridyl coordination cage was synthesized by the formal introduction of a carbon bridge between the coordinating pyridine rings. Structurally, the ruthenium(II) complex shows an almost perfect octahedral N6 coordination around the central Ru(II) metal ion. The investigation of the photophysical properties reveals a triplet metal-to-ligand charge transfer emission with an unprecedented quantum yield of 13% and a lifetime of 1.36 mus at room temperature and in the presence of air oxygen. An exceptional small energy gap between light absorption and light emission, or Stokes shift, was detected. Additionally, time-dependent density functional theory calculations were carried out in order to characterize the ground state and both the singlet and triplet excited states. The exceptional properties of the new compound open the perspective of exploiting terpyridyl-like ruthenium complexes in photochemical devices under ambient conditions.

Using precision peptide targeting to discrete cell organelles, it is demonstrated that Ru(ii) polypyridyl complexes are highly effective probes for stimulated emission depletion microscopy.