[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

Microporous networks based on boronate ester-capped iron(ii) clathrochelate complexes are described. The networks were obtained by covalent cross-linking of tetrabrominated clathrochelate complexes via Suzuki-Miyaura polycross-coupling reactions with diboronic acids, or by Sonogashira-Hagihara polycross-coupling of clathrochelate complexes with terminal alkyne functions and 1,3,5-tribromobenzene. The networks display permanent porosity with apparent Brunauer-Emmett-Teller surface areas of up to SABET = 593 m2 g-1. A clathrochelate complex based on an enantiopure dioximato ligand was used to prepare chiral networks. One of these networks was shown to preferentially absorb d-tryptophan over l-tryptophan.

Porous networks based on iron(ii) clathrochelate complexes

Crystallisation of inorganic salts containing 18-crown-6 from ionic liquids

Coordination cages based on organometallic half-sandwich complexes are of interest, because they can display unique structures and host properties. This communication describes the synthesis and structure of a cylindrical nanostructure containing six (p-cymene)Ru-II fragments. The complex was obtained by reaction of [(p-cymene)RuCl2](2) with a novel C-3-symmetrical ligand containing a triarylamine core and three dihydroxypyridine groups in its periphery. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Expanding the Size of Organometallic Nanostructures: A Hexanuclear (Cymene)Ru Cylinder with a Length of More Than 3 nm

The reaction of a tripodal ligand containing terminal 2,3-dihydroxypyridine groups with (arene)ruthenium(II) complexes resulted in the formation of cylindrical nanostructures.

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Breaking the symmetry: assembly of cylindrical nanostructures with a C3-symmetrical ligand.

Reaction of the diphosphanylamine 2,6-{(Ph2P)(2)N)(2)C5H3N with four equivalents of Au(tht)Cl (tht = tetrahydrothiophene) affords the tetragold complex 2,6{(ClAuPh2P)(2)N)(2)C5H3N in high yield. Decomposition of the tetragold compound results in the formation of the digold complex 2,6-{(ClAuPh2P)HN}(2)C5H3N and colloidal gold. A trigold intermediate, which contains a Au-Au interaction [2.9886(5) Angstrom] has been isolated, and while ultimately unstable, it is thought to be partially stabilised by virtue of the aurophilic nature of gold. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).

Rosario Scopelliti

Papers

Porous networks based on iron(ii) clathrochelate complexes

Crystallisation of inorganic salts containing 18-crown-6 from ionic liquids

Expanding the Size of Organometallic Nanostructures: A Hexanuclear (Cymene)Ru Cylinder with a Length of More Than 3 nm

Breaking the symmetry: assembly of cylindrical nanostructures with a C3-symmetrical ligand.

Isolation of an Intermediate during the Decomposition of a Tetragold-Phosphane Complex