Rare earths: jewels for functional materials of the future

Eliseeva, Svetlana V.,Bü,nzli, Jean-Claude G. Royal Society of Chemistry 2011 New journal of chemistry Vol.35 No.6

<P>In recent decades, rare earths have become vital to a wealth of advanced materials and technologies including catalysts, alloys, magnets, optics and lasers, rechargeable hydride batteries, electronics, economical lighting, wind- and solar-energy conversion, bio-analyses and imaging. In this perspective article we give a broad overview of rare earth resources and uses first and then of selected applications in dedicated fields such as telecommunications, lasers, photovoltaics (solar-energy conversion), lighting (fluorescent lamps and OLEDs), luminescent probes for bio-analyses and bio-imaging, as well as magnetism and magnetic refrigeration.</P> <P>Graphic Abstract</P><P>Rare-earth resources and uses are presented and selected applications in telecommunications, lasers, solar-energy conversion, lighting, bioanalyses, bioimaging, single-molecule magnets, and magnetic refrigeration are discussed. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c0nj00969e'> </P>

Biphenylene-bridged mesostructured organosilica as a novel hybrid host material for LnIII (Ln = Eu, Gd, Tb, Er, Yb) ions in the presence of 2-thenoyltrifluoroacetone

Biju, Silvanose,Eom, Yu Kyung,Bü,nzli, Jean-Claude G.,Kim, Hwan Kyu The Royal Society of Chemistry 2013 Journal of materials chemistry. C, Materials for o Vol.1 No.21

Lanthanide luminescence for functional materials and bio-sciences

Eliseeva, Svetlana V.,Bü,nzli, Jean-Claude G. Royal Society of Chemistry 2010 Chemical Society reviews Vol.39 No.1

<P>Recent startling interest for lanthanide luminescence is stimulated by the continuously expanding need for luminescent materials meeting the stringent requirements of telecommunication, lighting, electroluminescent devices, (bio-)analytical sensors and bio-imaging set-ups. This <I>critical review</I> describes the latest developments in (i) the sensitization of near-infrared luminescence, (ii) “soft” luminescent materials (liquid crystals, ionic liquids, ionogels), (iii) electroluminescent materials for organic light emitting diodes, with emphasis on white light generation, and (iv) applications in luminescent bio-sensing and bio-imaging based on time-resolved detection and multiphoton excitation (500 references).</P> <P>Graphic Abstract</P><P>Lighting, telecommunications, electroluminescent devices, (bio-)analytical sensors, live cell bio-imaging, all rely on lanthanide luminescence which illuminates our daily life. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=b905604c'> </P>

A Eu^III Tetrakis(β-diketonate) Dimeric Complex: Photophysical Properties, Structural Elucidation by Sparkle/AM1 Calculations, and Doping into PMMA Films and Nanowires

Biju, Silvanose,Freire, Ricardo O.,Eom, Yu Kyung,Scopelliti, Rosario,Bü,nzli, Jean-Claude G.,Kim, Hwan Kyu American Chemical Society 2014 Inorganic Chemistry Vol.53 No.16

<P>Reaction of Ln<SUP>III</SUP> with a tetrakis(diketone) ligand H<SUB>4</SUB>L [1,1′-(4,4′-(2,2-bis((4-(4,4,4-trifluoro-3-oxobutanoyl) phenoxy)methyl)propane-1,3-diyl)bis(oxy)bis(4,1-phenylene))bis(4,4,4-trifluorobutane-1,3-dione)] gives new podates which, according to mass spectral data and Sparkle/AM1 calculations, can be described as dimers, (NBu<SUB>4</SUB>[LnL])<SUB>2</SUB> (Ln = Eu, Tb, Gd:Eu), in both solid-state and dimethylformamide (DMF) solution. The photophysical properties of the Eu<SUP>III</SUP> podate are compared with those of the mononuclear diketonate (NBu<SUB>4</SUB>[Eu(BTFA)<SUB>4</SUB>], BTFA = benzoyltrifluoroacetonate), the crystal structure of which is also reported. The new Eu<SUP>III</SUP> dimeric complex displays bright red luminescence upon irradiation at the ligand-centered band in the range of 250–400 nm, irrespective of the medium. The emission quantum yields and the luminescence lifetimes of (NBu<SUB>4</SUB>[EuL])<SUB>2</SUB> (solid state: 51% ± 8% and 710 ± 2 μs; DMF: 31% ± 5% and 717 ± 1 μs) at room temperature are comparable to those obtained for NBu<SUB>4</SUB>[Eu(BTFA)<SUB>4</SUB>] (solid state: 60 ± 9% and 730 ± 5 μs; DMF: 30 ± 5% and 636 ± 1 μs). Sparkle/AM1 calculations were utilized for predicting the ground-state geometries of the Eu<SUP>III</SUP> dimer. Theoretical Judd–Ofelt and photoluminescence parameters, including quantum yields, predicted from this model are in good agreement with the experimental values, proving the efficiency of this theoretical approach implemented in the LUMPAC software (<uri xlink:href='http://lumpac.pro.br' xlink:type='simple'>http://lumpac.pro.br</uri>). The kinetic scheme for modeling energy transfer processes show that the main donor state is the ligand triplet state and that energy transfer occurs on both the <SUP>5</SUP>D<SUB>1</SUB> (44.2%) and <SUP>5</SUP>D<SUB>0</SUB> (55.8%) levels. Furthermore, the newly obtained Eu<SUP>III</SUP> complex was doped into a PMMA matrix to form highly luminescent films and one-dimensional nanowires having emission quantum yield as high as 67%–69% (doping concentration = 4% by weight); these materials display bright red luminescence even under sunlight, so that interesting photonic applications can be foreseen.</P><P>A red-emitting dimeric Eu<SUP>III</SUP> podate based on a tetrakis(β-diketonate) ligand emits highly monochromatic red light and features the highest quantum yield reported so far for dinuclear Eu<SUP>III</SUP> bis(β-diketonates); doping into a PMMA matrix results in thin films and one-dimensional nanowires, the luminescence of which can be seen under sunlight illumination.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/inocaj/2014/inocaj.2014.53.issue-16/ic500966z/production/images/medium/ic-2014-00966z_0012.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ic500966z'>ACS Electronic Supporting Info</A></P>

Optimizing Millisecond Time Scale Near-Infrared Emission in Polynuclear Chrome(III)-Lanthanide(III) Complexes

Aboshyan-Sorgho, Lilit,Nozary, Homayoun,Aebischer, Annina,Bü,nzli, Jean-Claude G.,Morgantini, Pierre-Yves,Kittilstved, Kevin R.,Hauser, Andreas,Eliseeva, Svetlana V.,Petoud, Sté,phane,Piguet American Chemical Society 2012 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.134 No.30

Sensitized near-IR luminescence of lanthanide complexes based on push-pull diketone derivatives

Baek, Nam Seob,Kim, Yong Hee,Eom, Yu Kyung,Oh, Jung Hwan,Kim, Hwan Kyu,Aebischer, Annina,Gumy, Fré,dé,ric,Chauvin, Anne-Sophie,Bü,nzli, Jean-Claude G. Royal Society of Chemistry 2010 Dalton Transactions Vol.39 No.6

<P>Lanthanide complexes with two push-pull diketone derivatives as sensitizers have been developed as synthons for near-infrared emitting materials. The ligand substituents consist of a carbazole moiety with hole-transport properties and an aromatic or heteroaromatic unit. According to quantitative NMR analysis and complementary HPLC experiments, the diketones are predominantly in their enolic form in polar solvents such as THF and MeCN at room temperature. The preferred <I>cis</I>-enol form contributes strongly to the binding of lanthanide ions (Ln = Nd, Gd, Er). The resulting tris(diketonate) ternary complexes with terpyridine (Ln = Nd, Er) display sizeable near-IR emission with long luminescence lifetimes.</P> <P>Graphic Abstract</P><P>Lanthanide complexes with two push-pull diketone derivatives as sensitizers have been developed as synthons for near-infrared emitting materials. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=b915893f'> </P>

Color and Brightness Tuning in Heteronuclear Lanthanide Terephthalate Coordination Polymers

Haquin, Victor,Etienne, Mael,Daiguebonne, Carole,Freslon, Sté,phane,Calvez, Guillaume,Bernot, Kevin,Le Pollè,s, Laurent,Ashbrook, Sharon E.,Mitchell, Martin R.,Bü,nzli, Jean‐,Cla WILEY‐VCH Verlag 2013 European journal of inorganic chemistry Vol.2013 No.20

<P><B>Abstract</B></P><P>Heteronuclear lanthanide terephthalate coordination polymers with the general chemical formula [Ln<SUB>2–2<I>x</I></SUB>Ln′<SUB>2<I>x</I></SUB>(bdc)<SUB>3</SUB>(H<SUB>2</SUB>O)<SUB>4</SUB>]<SUB>∞</SUB>, for which bdc<SUP>2–</SUP> symbolizes benzene‐1,4‐dicarboxylate (or terephthalate) and Ln and Ln′ represent trivalent rare earth ions, were synthesized and structurally characterized. Analysis of the Y/Lu compounds by <SUP>89</SUP>Y and <SUP>13</SUP>C solid‐state NMR spectroscopy was carried out, and the results support the hypothesis of randomly distributed lanthanide ions. The spectroscopic and colorimetric properties of this family of compounds were investigated in detail. The resulting data demonstrate that this series of compounds presents highly tunable luminescence properties and clearly indicate that intermetallic deactivation processes play an important role in the emission mechanism. Playing with intermetallic distances allows one to tune the color and the brightness of the lanthanide emission in these coordination polymers.</P>

Bioconjugated lanthanide luminescent helicates as multilabels for lab-on-a-chip detection of cancer biomarkers

Ferná,ndez-Moreira, Vanesa,Song, Bo,Sivagnanam, Venkataragavalu,Chauvin, Anne-Sophie,Vandevyver, Caroline D. B.,Gijs, Martin,Hemmilä,, Ilkka,Lehr, Hans-Anton,Bü,nzli, Jean-Claude G. Royal Society of Chemistry 2010 The Analyst Vol.135 No.1

<P>The lanthanide binuclear helicate [Eu<SUB>2</SUB>(L<SUP>C2(CO<SUB>2</SUB>H)</SUP>)<SUB>3</SUB>] is coupled to avidin to yield a luminescent bioconjugate <B>EuB1</B> (<I>Q</I> = 9.3%, <I>τ</I>(<SUP>5</SUP>D<SUB>0</SUB>) = 2.17 ms). MALDI/TOF mass spectrometry confirms the covalent binding of the Eu chelate and UV-visible spectroscopy allows one to determine a luminophore/protein ratio equal to 3.2. Bio-affinity assays involving the recognition of a mucin-like protein expressed on human breast cancer MCF-7 cells by a biotinylated monoclonal antibody 5D10 to which <B>EuB1</B> is attached <I>via</I> avidin-biotin coupling demonstrate that (i) avidin activity is little affected by the coupling reaction and (ii) detection limits obtained by time-resolved (TR) luminescence with <B>EuB1</B> and a commercial Eu-avidin conjugate are one order of magnitude lower than those of an organic conjugate (FITC-streptavidin). In the second part of the paper, conditions for growing MCF-7 cells in 100–200 µm wide microchannels engraved in PDMS are established; we demonstrate that <B>EuB1</B> can be applied as effectively on this lab-on-a-chip device for the detection of tumour-associated antigens as on MCF-7 cells grown in normal culture vials. In order to exploit the versatility of the ligand used for self-assembling [Ln<SUB>2</SUB>(L<SUP>C2(CO<SUB>2</SUB>H)</SUP>)<SUB>3</SUB>] helicates, which sensitizes the luminescence of both Eu<SUP><SMALL>III</SMALL></SUP> and Tb<SUP><SMALL>III</SMALL></SUP> ions, a dual on-chip assay is proposed in which estrogen receptors (ERs) and human epidermal growth factor receptors (Her2/<I>neu</I>) can be simultaneously detected on human breast cancer tissue sections. The Ln helicates are coupled to two secondary antibodies: ERs are visualized by red-emitting <B>EuB4</B> using goat anti-mouse IgG and Her2/<I>neu</I> receptors by green-emitting <B>TbB5</B> using goat anti-rabbit IgG. The fact that the assay is more than 6 times faster and requires 5 times less reactants than conventional immunohistochemical assays provides essential advantages over conventional immunohistochemistry for future clinical biomarker detection.</P> <P>Graphic Abstract</P><P>Lanthanide luminescent bioprobes (LLBs) combined with microfluidics and lab-on-a-chip technology lead to fast dual assays of cancerous tissue biomarkers. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=b922124g'> </P>