[신간의 별자리x] 우리/미술, 그리고 ‘슬픔의 박물관’

Today's best perovskite solar cells use a mixture of formamidinium and methylammonium as the monovalent cations. With the addition of inorganic cesium, the resulting triple cation perovskite compositions are thermally more stable, contain less phase impurities and are less sensitive to processing conditions. This enables more reproducible device performances to reach a stabilized power output of 21.1% and ∼18% after 250 hours under operational conditions. These properties are key for the industrialization of perovskite photovoltaics.

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Cesium-containing triple cation perovskite solar cells: improved stability, reproducibility and high efficiency

Lanthanide ions possess fascinating optical properties and their discovery, first industrial uses and present high technological applications are largely governed by their interaction with light. Lighting devices (economical luminescent lamps, light emitting diodes), television and computer displays, optical fibres, optical amplifiers, lasers, as well as responsive luminescent stains for biomedical analysis, medical diagnosis, and cell imaging rely heavily on lanthanide ions. This critical review has been tailored for a broad audience of chemists, biochemists and materials scientists; the basics of lanthanide photophysics are highlighted together with the synthetic strategies used to insert these ions into mono- and polymetallic molecular edifices. Recent advances in NIR-emitting materials, including liquid crystals, and in the control of luminescent properties in polymetallic assemblies are also presented. (210 references.)

Taking advantage of luminescent lanthanide ions

All of the cations currently used in perovskite solar cells abide by the tolerance factor for incorporation into the lattice. We show that the small and oxidation-stable rubidium cation (Rb + ) can be embedded into a “cation cascade” to create perovskite materials with excellent material properties. We achieved stabilized efficiencies of up to 21.6% (average value, 20.2%) on small areas (and a stabilized 19.0% on a cell 0.5 square centimeters in area) as well as an electroluminescence of 3.8%. The open-circuit voltage of 1.24 volts at a band gap of 1.63 electron volts leads to a loss in potential of 0.39 volts, versus 0.4 volts for commercial silicon cells. Polymer-coated cells maintained 95% of their initial performance at 85°C for 500 hours under full illumination and maximum power point tracking.

https://science.sciencemag.org/content/sci/early/2016/09/28/science.aah5557.full.pdf

Incorporation of rubidium cations into perovskite solar cells improves photovoltaic performance

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 critical review 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).

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Lanthanide luminescence for functional materials and bio-sciences

Synthetic studies of bimetallic uranium nitride complexes with the N(SiMe3)2 ligand have generated a new nitride complex of U(III), which is highly reactive toward C-H bonds and H2. Treatment of the previously reported U(IV)/U(IV) nitride complex [Na(DME)3][((Me3Si)2N)2U(μ-N)(μ-κ2:CN-CH2SiMe2NSiMe3)U(N(SiMe3)2)2] (DME = 1,2-dimethoxyethane), 1, with 2 equiv of HNEt3BPh3 yielded the cationic U(IV)/U(IV) nitride complex, [{((Me3Si)2N)2U(THF)}2(μ-N)][BPh4] (THF = tetrahydrofuran), 3, by successive protonolysis of one N(SiMe3)2 ligand and the uranium-methylene bond. Reduction of 3 with KC8 afforded a rare example of a U(III) nitride, namely, the U(III)/U(IV) complex, [{((Me3Si)2N)2U(THF)}2(μ-N)], 4. Complex 4 is highly reactive and undergoes 1,2-addition of the C-H bond of the N(SiMe3)2 ligand across the uranium-nitride moiety to give the U(III)/U(IV) imide cyclometalate complex, [((Me3Si)2N)2(THF)U(μ-NH)(μ-κ2:C,N-CH2SiMe2NSiMe3)U(N(SiMe3)2))(THF)], 5. Complex 4 also reacts with toluene at -80 °C to yield an inverse sandwich imide complex arising from C-H bond activation of toluene, [{((Me3Si)2N)2U(THF)}2(μ-N)][{((Me3Si)2N)3U(μ-NH)U(N(SiMe3)2)}2(C7H8)], 6. Complex 4 effects the heterolytic cleavage of the C-H of phenylacetylene to yield the imide acetylide [{((Me3Si)2N)2U(THF)}2(μ-N)][((Me3Si)2N)2U(η1-CCPh)(μ2-NH)(μ2-η2:η1-CCPh)U(N(SiMe3)2)2], 7. Complex 4 also reacts with H2 to produce an imide hydride U(III)/U(IV) complex, [{((Me3Si)2N)2U(THF)}2(μ-NH)(μ-H)], 9. These data demonstrate that nitride complexes of U(III) are accessible with amide ligands and show the high reactivity of molecular U(III) nitrides in C-H bond activation.

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C–H Bond Activation by an Isolated Dinuclear U(III)/U(IV) Nitride

Methods for the synthesis of bimetallic complexes in which two different metal fragments are connected by three chloro or bromo bridges are reported. The reactions are general, fast, and give rise to structurally defined products in quantitative yields. Therefore, they are ideally suited for generating a library of homo- and heterobimetallic complexes in a combinatorial fashion. This is of special interest for applications in homogeneous catalysis. Selected members of this library were synthesized and comprehensively characterized; single-crystal X-ray analyses were performed for 15 new bimetallic compounds.

Combinatorial synthesis of bimetallic complexes with three halogeno bridges.

Beyond Click-Chemistry: Transformation of Azides with Cyclopentadienyl Ruthenium Complexes

The homo- and heterobimetallic complexes [Cp*Ru(m-Cl)3-ML] [LM = (C6H6)Ru, (cymene)Ru, (1,3,5-C6H3iPr3)Ru, Cp*Rh, Cp*Ir] were prepd. by reaction of [Cp*Ru(m-OMe)]2 with Me3SiCl and subsequent addn. of [LMCl2]2. The complexes [Cp*Ru(m-Cl)3Ru(cymene)] and [Cp*Ru(m-Cl)3-IrCp*] were characterized by single-crystal X-ray analyses. In crossover expts. with [Cp*Rh(m-Cl)3RuCl(PPh3)2] and [Cp*Ru(m-Cl)3Ru(1,3,5-C6H3iPr3)] in CD2Cl2, a dynamic equil. with the complexes [Cp*Rh(m-Cl)3RuCp*] and [(1,3,5-C6H3iPr3)Ru(m-Cl)3RuCl(PPh3) 2] was rapidly established, demonstrating the kinetic lability of the triple chloro bridge. Upon reaction of [Cp*Rh(m-Cl)3RuCp*] with benzene, the ionic complex [Cp*Ru(C6H6)][Cp*RhCl3] was formed, which was characterized by X-ray crystallog.

Rosario Scopelliti

Papers

C–H Bond Activation by an Isolated Dinuclear U(III)/U(IV) Nitride

Combinatorial synthesis of bimetallic complexes with three halogeno bridges.

Beyond Click-Chemistry: Transformation of Azides with Cyclopentadienyl Ruthenium Complexes

Synthesis, Structure and Reactivity of Homo‐ and Heterobimetallic Complexes of the General Formula [CpRu(μ‐Cl)3ML] [LM = (arene)Ru, CpRh, Cp*Ir]

Complexation associated rearrangement of iminobiphosphines to diphosphinoamines

Rosario Scopelliti

Papers

C–H Bond Activation by an Isolated Dinuclear U(III)/U(IV) Nitride

Combinatorial synthesis of bimetallic complexes with three halogeno bridges.

Beyond Click-Chemistry: Transformation of Azides with Cyclopentadienyl Ruthenium Complexes

Synthesis, Structure and Reactivity of Homo‐ and Heterobimetallic Complexes of the General Formula [Cp*Ru(μ‐Cl)3ML] [LM = (arene)Ru, Cp*Rh, Cp*Ir]

Complexation associated rearrangement of iminobiphosphines to diphosphinoamines

Synthesis, Structure and Reactivity of Homo‐ and Heterobimetallic Complexes of the General Formula [CpRu(μ‐Cl)3ML] [LM = (arene)Ru, CpRh, Cp*Ir]