The design principles that guide the creation of responsive lanthanide luminescent probes are defined, classified and exemplified.

The syntheses and photophysical behaviour of nine, strongly luminescent nonadentate Eu(III) complexes are reported. Each complex is based on N-functionalised 1,4,7triazacyclononane, and linkage to other groups or targeting vectors can occur either via amide bond formation to a coordinated pyridine p-aminopropyl group or via a nucleophilic substitution reaction involving thiol attack on a metal coordinated p-nitropyridyl moiety. Evidence is presented in favour of the latter conjugation strategy, as parallel work with maleimide conjugates was complicated or compromised by the propensity to undergo postconjugation thiol exchange or succinimide ring hydrolysis reactions. Confocal microscopy and spectral imaging studies revealed that the peptide conjugate of AcCFFKDEL was found to localise selectively in the endoplasmic reticulum of mouse fibroblast cells, whereas the related maleimide conjugate was only observed in cellular lysosomes.

A set of four luminescent EuIII complexes bearing an extended aryl‐alkynylpyridine chromophore has been studied, showing very different pH‐dependent behaviour in their absorption and emission spectral response. For two complexes with pKa values of 6.45 and 6.20 in protein‐containing solution, the emission lifetime increases very significantly following protonation. By varying the gate time during signal acquisition, the ‘switch‐on’ intensity ratio could be optimised, and enhancement factors of between 250 to 1330 were measured between pH 8 and 4. The best‐behaved probe showed no significant emission dependence on the concentration of endogenous cations, reductants, and serum albumin. It was examined in live‐cell imaging studies to monitor time‐dependent lysosomal acidification, for which the increase in observed image brightness due to acidification was a factor of 50 in NIH‐3T3 cells.

We report the design and evaluation of pH responsive luminescent europium(III) probes that allow conjugation to targeting vectors to monitor receptor internalisation in cells. The approach adopted here can be...

Examination of total emission and circularly polarised luminescence (CPL) spectra of three 9-coordinate Eu(III) complexes with well-defined speciation shows that the ligand fields of these C3 symmetric complexes are extremely...

Tridentate ligands, easily synthesised by condensation reactions of simple starting materials, can be used to prepare Pt(ii) complexes that are luminescent in solution, emitting in the red or deep-red spectral region, according to the substituents.

A series of cationic and neutral p−Br and p−NO2 pyridine substituted Eu(III) and Gd(III) coordination complexes serve as versatile synthetic intermediates. Nucleophilic aromatic substitution occurs readily at the para position under mild conditions, allowing C−N and C−C bond forming reactions to take place, permitting the introduction of azide, amino and alkynyl substituents. For Eu(III) complexes, this approach allows late stage tuning of absorption and emission spectral properties, exemplified by the lowering of the energy of an LMCT transition accompanied by a reduction in the Eu−Npy bond length. Additionally, these complexes provide direct access to the corresponding Eu(II) analogues. With the Gd(III) series, the nature of the p‐substituent does not significantly change the EPR properties (linewidth, relaxation times), as required for their development as EPR spin probes that can be readily conjugated to biomolecules under mild conditions.

The relative sensitivity of structurally related Eu(III) complexes to quenching by electron and energy transfer processes has been compared. In two sets of 9-coordinate complexes based on 1,4,7-triazacyclonane, the Eu...