Chromophore-labelled, luminescent platinum complexes: syntheses, structures, and spectroscopic properties

Ligands based upon 4-carboxamide-2-phenylquinoline derivatives have been synthesised with solubilising octyl hydrocarbon chains and tethered aromatic chromophores to give naphthyl (HL2), anthracenyl (HL3) and pyrenyl (HL4) ligand variants, together with a non-chromophoric analogue (HL1) for comparison. 1H NMR spectroscopic studies of the ligands showed that two non-interchangeable isomers exist for HL2 and HL4 while only one isomer exists for HL1 and HL3. Supporting DFT calculations on HL4 suggest that the two isomers may be closely isoenergetic with a relatively high barrier to exchange of ca. 100 kJ mol−1. These new ligands were cyclometalated with Pt(II) to give complexes [Pt(L1–4)(acac)] (acac = acetylacetonate). The spectroscopically characterised complexes were studied using multinuclear NMR spectroscopy including 195Pt{1H} NMR studies which revealed δPt ca. −2785 ppm for [Pt(L1–4)(acac)]. X-ray crystallographic studies were undertaken on [Pt(L3)(acac)] and [Pt(L4)(acac)], each showing the weakly distorted square planar geometry at Pt(II); the structure of [Pt(L3)(acac)] showed evidence for intermolecular Pt–Pt interactions. The UV-vis. absorption studies show that the spectral profiles for [Pt(L2–4)(acac)] are a composite of the organic chromophore centred bands and a broad 1MLCT (5d → π*) band (ca. 440 nm) associated with the complex. Luminescence studies showed that complexes [Pt(L2–4)(acac)] are dual emissive with fluorescence characteristic of the tethered fluorophore and long-lived phosphorescence attributed to 3MLCT emission. In the case of the pyrenyl derivative, [Pt(L4)(acac)], the close energetic matching of the 3MLCT and 3LCpyr excited states led to an elongation of the 3MLCT emission lifetime (τ = 42 μs) under degassed solvent conditions, suggestive of energy transfer processes between the two states

Correction: An exploration of homo- and heterometallic UO22+ hybrid materials containing chelidamic acid: synthesis, structure, and luminescence studies

Correction for ‘An exploration of homo- and heterometallic UO22+ hybrid materials containing chelidamic acid: synthesis, structure, and luminescence studies’ by Paula M. Cantos et al., CrystEngComm, 2013, 15, 9039–9051, DOI: 10.1039/C3CE41655K

Synthesis and characterisation of phosphorescent rhenium(I) complexes of hydroxy- and methoxy-substituted imidazo[4,5- f ]-1,10-phenanthroline ligands

Eight new fluorescent ligands (L1-L8) derived from the fused imidazo[4,5-f]-1,10-phenanthroline core, have been synthesised utilising a one-pot methodology. The ligands include two points of structural variety, allowing multiply-substituted aryl groups (including hydroxy and methoxy moieties) to be attached to the ligand core. The ligands L1-L8 are fluorescent (λem = 399–426 nm) and react with pentacarbonylbromorhenium to give coordination complexes of the form fac-[ReBr(CO)3(NˆN)] (where NˆN = L1-L8). The complexes were characterised using a variety of spectroscopic and analytical techniques, including single crystal X-ray diffraction studies on two examples. The rhenium complexes were all found to be luminescent, revealing classical 3MLCT emission at 579–587 nm in aerated solution with corresponding lifetimes in the range 149–166 ns

Using lanthanide ions in molecular bioimaging

Trivalent lanthanide ions offer remarkable opportunities in the design of bioimaging agents: this review presents an accessible discussion of their application in both optical and magnetic resonance imaging. Aspects of molecular design, control over key physical properties and biological compatibility are discussed in this context, together with developments and opportunities as responsive probes and in multimodal imaging

Synthesis and luminescent properties of hetero-bimetallic and hetero-trimetallic Ru( ii )/Au( i ) or Ir( iii )/Au( i ) complexes

A series of Ru(ii) and Ir(iii) based photoluminescent complexes were synthesised that incorporate an ancillary 2,2′-bipyridine ligand adorned with either one or two pendant N-methyl imidazolium groups. These complexes have been fully characterised by an array of spectroscopic and analytical techniques. One Ir(iii) example was unequivocally structurally characterised in the solid state using single crystal X-ray diffraction confirming the proposed formulation and coordination sphere. These complexes were then transformed into their heterometallic, Au(i)-containing, analogues in two steps to yield either bi- or trimetallic complexes that integrate {Au(PPh3)}+ units. X-ray diffraction was used to corroborate the solid state structure of the hetero bimetallic complex, based upon a Ru(ii)–Au(i) species. The heterometallic complexes all displayed red photoluminescent features (λem = 616–629 nm) that were consistent with the parent Ru(ii) or Ir(iii) lumophores in each case. The modulation of the emission from the Ru(ii)–Au(i) complexes was much more strongly evident than for the Ir(iii)–Au(i) analogues, which is ascribed to the inherent differences in the specific triplet excited state character of the emitting states within each heterometallic species

Nurse staffing and patient outcomes: strengths and limitations of the evidence to inform policy and practice. A review and discussion paper based on evidence reviewed for the National Institute for Health and Care Excellence safe staffing guideline development

A large and increasing number of studies have reported a relationship between low nurse staffing levels and adverse outcomes, including higher mortality rates. Despite the evidence being extensive in size, and having been sometimes described as “compelling” and “overwhelming”, there are limitations that existing studies have not yet been able to address. One result of these weaknesses can be observed in the guidelines on safe staffing in acute hospital wards issued by the influential body that sets standards for the National Health Service in England, the National Institute for Health and Care Excellence (NICE), which concluded there is insufficient good quality evidence available to fully inform practice. In this paper we explore this apparent contradiction. After summarising the evidence review that informed the NICE guideline on safe staffing and related evidence, we move on to discussing the complex challenges that arise when attempting to apply this evidence to practice. Among these, we introduce the concept of endogeneity, a form of bias in the estimation of causal effects. Although current evidence is broadly consistent with a cause and effect relationship, endogeneity means that estimates of the size of effect, essential for building an economic case, may be biased and in some cases qualitatively wrong. We expand on three limitations that are likely to lead to endogeneity in many previous studies: omitted variables, which refers to the absence of control for variables such as medical staffing and patient case mix; simultaneity, which occurs when the outcome can influence the level of staffing just as staffing influences outcome; and common-method variance, which may be present when both outcomes and staffing levels variables are derived from the same survey. Thus while current evidence is important and has influenced policy because it illustrates the potential risks and benefits associated with changes in nurse staffing, it may not provide operational solutions. We conclude by posing a series of questions about design and methods for future researchers who intend to further explore this complex relationship between nurse staffing levels and outcomes. These questions are intended to reflect on the potential added value of new research given what is already known, and to encourage those conducting research to take opportunities to produce research that fills gaps in the existing knowledge for practice. By doing this we hope that future studies can better quantify both the benefits and costs of changes in nurse staffing levels and, therefore, serve as a more useful tool for those delivering services. <br/

2-(Thienyl)quinoxaline derivatives and their application in Ir( iii ) complexes yielding tuneable deep red emitters †

The synthesis and characterisation of eleven different 2-(thienyl)quinoxaline species that incorporate different points of functionality, including at the thiophene or quinoxaline rings, are described. These species display variable fluorescence properties in the visible region (λem = 401–491 nm) depending upon the molecular structures and extent of conjugation. The series of 2-(thienyl)quinoxaline species were then investigated as cyclometalating agents for Ir(iii) to yield [Ir(C^N)2(bipy)]PF6 (where C^N = the cyclometalated ligand; bipy = 2,2′-bipyridine). Eight complexes were successfully isolated and fully characterised by an array of spectroscopic and analytical techniques. Two Ir(iii) examples were structurally characterised in the solid state using single crystal X-ray diffraction; both structures confirmed the proposed formulations and coordination spheres in each case showing that the thiophene coordinates via a Ir–C bond. The photophysical properties of the complexes revealed that each complex is luminescent under ambient conditions with a range of emission wavelengths observed (665–751 nm) indicating that electronic tuning can be achieved via both the thienyl and quinoxaline moieties

Polycationic Ru(II) luminophores: syntheses, photophysics, and application in electrostatically driven sensitization of lanthanide luminescence

A series of photoluminescent Ru(II) polypyridine complexes have been synthesized in a manner that varies the extent of the cationic charge. Two ligand systems (L1 and L2), based upon 2,2′-bipyridine (bipy) mono- or difunctionalized at the 5- or 5,5′-positions using N-methylimidazolium groups, were utilized. The resulting Ru(II) species therefore carried +3, +4, +6, and +8 complex moieties based on a [Ru(bipy)3]2+ core. Tetra-cationic [Ru(bipy)2(L2)][PF6]4 was characterized using XRD, revealing H-bonding interactions between two of the counteranions and the cationic unit. The ground-state features of the complexes were found to closely resemble those of the parent unfunctionalized [Ru(bipy)3]2+ complex. In contrast, the excited state properties produce a variation in emission maxima, including a bathochromic 44 nm shift of the 3MLCT band for the tetra-cationic complex; interestingly, further increases in overall charge to +6 and +8 produced a hypsochromic shift in the 3MLCT band. Supporting DFT calculations suggest that the trend in emission behavior may, in part, be due to the precise nature of the LUMO and its localization. The utility of a photoactive polycationic Ru(II) complex was then demonstrated through the sensitization of a polyanionic Yb(III) complex in free solution. The study shows that electrostatically driven ion pairing is sufficient to facilitate energy transfer between the 3MLCT donor state of the Ru(II) complex and the accepting 2F5/2 excited state of Yb(III)