Luminescence tuning of MOFs via ligand to metal and metal to metal energy transfer by co-doping of 2∞[Gd2Cl6(bipy)3]*2bipy with europium and terbium

The series of anhydrous lanthanide chlorides LnCl3, Ln=Pr–Tb, and 4,4'-bipyridine (bipy) constitute isotypic MOFs of the formula 2∞[Ln2Cl6(bipy)3]*2bipy. The europium and terbium containing compounds both exhibit luminescence of the referring trivalent lanthanide ions, giving a red luminescence for Eu3+ and a green luminescence for Tb3+ triggered by an efficient antenna effect of the 4,4'-bipyridine linkers. Mixing of different lanthanides in one MOF structure was undertaken to investigate the potential of this MOF system for colour tuning of the luminescence. Based on the gadolinium containing compound, co-doping with different amounts of europium and terbium proves successful and yields solid solutions of the formula 2∞[Gd2-x-yEuxTbyCl6(bipy)3]*2bipy (1–8), 0≤x, y≤0.5. The series of MOFs exhibits the opportunity of tuning the emission colour in-between green and red. Depending on the atomic ratio Gd:Eu:Tb, the yellow region was covered for the first time for an oxygen/carboxylate-free MOF system. In addition to a ligand to metal energy transfer (LMET) from the lowest ligand-centered triplet state of 4,4'-bipyridine, a metal to metal energy transfer (MMET) between 4f-levels from Tb3+ to Eu3+ is as well vital for the emission colour. However, no involvement of Gd3+ in energy transfers is observed rendering it a suitable host lattice ion and connectivity centre for diluting the other two rare earth ions in the solid state. The materials retain their luminescence during activation of the MOFs for microporosity

Recruitment patterns, low cannibalism and reduced interspecific predation contribute to high invasion success of two Pacific crabs in northwestern Europe

Life-history traits and interactions with native species play an important role for the successful establishment of non-native species in new habitats. We investigated the recent successful invasion of the Pacific crabs Hemigrapsus takanoi and H. sanguineus to the southeastern North Sea coast with respect to their recruitment patterns, as well as interactions of juvenile with sub-adult individuals among the Pacific crabs and with native shore crabs Carcinus maenas. A field survey of juvenile native and introduced crab abundances (carapace width 1.4–10 mm) was conducted in the northern Wadden Sea, spanning 24 months from 2014 to 2016. The survey revealed different seasonal recruitment patterns of native C. maenas and both introduced Hemigrapsus species. Native shore crabs showed a single recruitment peak from June to July, while Hemigrapsus spp. mainly recruited from August to early September, but recruits occurred in low densities throughout the winter until the end of the following spring season. Field experiments on the effects of larger crabs on the recruitment intensity showed that recruitment of H. takanoi was enhanced by the presence of larger congeners, but remained unaffected by larger C. maenas. Recruitment of juvenile C. maenas, by contrast, was reduced by the presence of larger Hemigrapsus spp. Additional laboratory experiments revealed high rates of cannibalism on newly recruited C. maenas by subadult conspecifics as well as strong predation by larger Hemigrapsus spp. In contrast, newly recruited Hemigrapsus spp. had a much lower risk of being preyed on by subadult conspecifics and native shore crabs. Our results suggest that the timing of recruitment in combination with low intraspecific competition and reduced predation pressure by native shore crabs are crucial for the rapid and ongoing establishment of Hemigrapsus spp. in the Wadden Sea

Molecularly imprinted conductive polymers for controlled trafficking of neurotransmitters at solid–liquid interfaces

We realize a molecularly imprinted polymer (MIP) which is imprinted with the retinal neurotransmitter glutamate. The films prepared by electrochemical deposition have a smooth surface with a granular morphology as observed using an atomic force microscope. Multiple reflection attenuated total reflection infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) are used to chemically confirm the imprint of a neurotransmitter in the MIP at the solid–liquid and the solid–air interface, respectively. Fluorescence spectroscopy using the dye fluorescamine is used to monitor the changes in neurotransmitter concentration in various solvents induced by application of voltage to the MIP. By controlling neurotransmitter trafficking across a solid–liquid interface with voltage, we suggest the possibility of using such a neurotransmitter imprinted MIP for chemical stimulation of retinal neurons. The current state of the art approach to restore sight in certain cases of blindness is the replacement of damaged photoreceptors by a subretinal implant consisting of light-sensitive photodiodes. Thus a future perspective of our work would be to chemically stimulate the neurons by replacing the photodiodes in the subretinal implant by the neurotransmitter imprinted polymer film

A closer look into two-step perovskite conversion with X-ray scattering

Recently, hybrid perovskites have gathered much interest as alternative materials for the fabrication of highly efficient and cost-competitive solar cells; however, many questions regarding perovskite crystal formation and deposition methods remain. Here we have applied a two-step protocol where a crystalline PbI2 precursor film is converted to MAPbI3–xClx perovskite upon immersion in a mixed solution of methylammonium iodide and methylammonium chloride. We have investigated both films with grazing incidence small-angle X-ray scattering to probe the inner film morphology. Our results demonstrate a strong link between lateral crystal sizes in the films before and after conversion, which we attribute to laterally confined crystal growth. Additionally, we observe an accumulation of smaller grains within the bulk in contrast with the surface. Thus, our results help to elucidate the crystallization process of perovskite films deposited via a two-step technique that is crucial for controlled film formation, improved reproducibility, and high photovoltaic performance

Air-stable Solid-state Photoluminescence Standards for Quantitative Measurements Based on 4'-phenyl-2,2':6',2''-Terpyridine Complexes with Trivalent Lanthanides

Correct photoluminescence quantum yield (PLQY) determination in the solid state is vital for numerous application fields, such as photovoltaics, solid lighting or the development of phosphors. In order to increase the limited number of suitable standards for such determinations, two new Ln 3+ -based complexes with 4′-phenyl-2,2′ : 6′,2"-terpyridine γ-[Ln 4 (OAc) 12 (ptpy) 2 ] ( 1-Eu with europium and 1-Tb with terbium) are presented. The corresponding complexes show solid-state QYs of 58(4) % and 46(3) %, respectively, exhibiting broadband absorption in the UV range from 380-200 nm. As Ln 3+ ions in general exhibit narrow f - f transitions, spectral regions with a broadness of 20-35 nm can be checked. Both complexes have suitable thermal stability, up to 270 °C, and are stable with respect to air and humidity, for 1-Eu up to 75 % and for 1-Tb up to 53 % relative humidity. These complexes are altogether suitable as standards to increase the reliability of PLQY determination and proposed to be used for a relative PLQY determination in the solid stat

From nodal liquid to nodal Mottness in a frustrated Hubbard model

We investigate the physics of frustrated 3-leg Hubbard ladders in the band limit, when hopping across the ladder's rungs (t$_{\perp}$) is of the same order as hopping along them (t) much greater than the onsite Coulomb repulsion (U). We show that this model exhibits a striking electron-hole asymmetry close to half-filling: the hole-doped system at low temperatures develops a Resonating Valence Bond (RVB)-like d-wave gap (pseudogap close to ($\pi$,0)) coinciding with gapless nodal excitations (nodal liquid); in contrast, the electron-doped system is seen to develop a Mott gap at the nodes, whilst retaining a metallic character of its majority Fermi surface. At lower temperatures in the electron-doped case, d-wave superconducting correlations -- here, coexisting with gapped nodal excitations -- are already seen to arise. Upon further doping the hole-doped case, the RVB-like state yields to d-wave superconductivity. Such physics is reminiscent of that exhibited by the high temperature cuprate superconductors--notably electron-hole asymmetry as noted by Angle Resolved PhotoEmission Spectroscopy (ARPES) and the resistivity exponents observed. This toy model also reinforces the importance of a more thorough experimental investigation of the known 3-leg ladder cuprate systems, and may have some bearing on low dimensional organic superconductors.Comment: 26 pages, 16 figure

Real time investigations during sputter deposition for tailoring optical properties of metal-polymer interfaces

Poster presented at the 16th International Conference on Small-Angle Scattering, held on 13-18th September, 2015, Berlin (Germany).Tailoring optoelectronic properties of metal-polymer interfaces using self-assembly of nanoparticles is of crucial importance in organic electronics and organic photovoltaics [1]. In particular, metal sputter deposition on block-co-polymers is one widely used method to fabricate nanostructured metal layers on a large scale exploiting the selective wetting and doping of metals on polystyrene domains [2,3]. In order to obtain full control over the nanostructural evolution at the metal-polymer interface and its impact on optoelectronic properties, we employed a combination of in situ time-resolved microfocus Grazing Incidence Small Angle X-ray Scattering (μGISAXS) with in situ UV/Vis Specular Reflectance Spectroscopy (SRS) during sputter deposition of gold (Au) on thin polystyrene films (PS). We monitored the evolution of the metallic layer morphology according to changes in the key scattering features by geometrical modeling [4] and correlate the nanostructural development to optical properties. The changes of optoelectronic properties induced by metal nanoparticle growth during the sputter deposition process were exemplarily monitored using SRS. The morphological characterization is complemented by X-ray reflectivity and electron microscopy. This enables us to identify the different growth regimes including their specific thresholds and permits better understanding of the growth kinetics of gold clusters and their self-organization into complex nanostructures on polymer substrates. Thus, our findings are of great interest for applications in organic photovoltaics [5] and organic electronics, which benefit from tailored metal-polymer interfaces

Metamagnetism and critical fluctuations in high quality single crystals of the bilayer ruthenate Sr3Ru2O7

We report the results of low temperature transport, specific heat and magnetisation measurements on high quality single crystals of the bilayer perovskite Sr3Ru2O7, which is a close relative of the unconventional superconductor Sr2RuO4. Metamagnetism is observed, and transport and thermodynamic evidence for associated critical fluctuations is presented. These relatively unusual fluctuations might be pictured as variations in the Fermi surface topography itself. No equivalent behaviour has been observed in the metallic state of Sr2RuO4.Comment: 4 pages, 4 figures, Revtex 3.