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Rosario Scopelliti

Bio: Rosario Scopelliti is an academic researcher from École Polytechnique Fédérale de Lausanne. The author has contributed to research in topics: Ligand & Ionic liquid. The author has an hindex of 65, co-authored 394 publications receiving 13844 citations.
Topics: Ligand, Ionic liquid, Chemistry, Ruthenium, Lanthanide


Papers
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Journal ArticleDOI
TL;DR: In this article, a molecularly engineered hole-transport material with a simple dissymmetric fluorene-dithiophene core substituted by N,N-di-p-methoxyphenylamine donor groups is presented.
Abstract: Solution-processable perovskite solar cells have recently achieved certified power conversion efficiencies of over 20%, challenging the long-standing perception that high efficiencies must come at high costs. One major bottleneck for increasing the efficiency even further is the lack of suitable hole-transporting materials, which extract positive charges from the active light absorber and transmit them to the electrode. In this work, we present a molecularly engineered hole-transport material with a simple dissymmetric fluorene–dithiophene (FDT) core substituted by N,N-di-p-methoxyphenylamine donor groups, which can be easily modified, providing the blueprint for a family of potentially low-cost hole-transport materials. We use FDT on state-of-the-art devices and achieve power conversion efficiencies of 20.2% which compare favourably with control devices with 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene (spiro-OMeTAD). Thus, this new hole transporter has the potential to replace spiro-OMeTAD. The efficiency of perovskite solar cells is limited by the performance of the hole-transport material, which extracts charges from the active layer. Here, a molecularly engineered hole transporter with performance comparable to spiro-OMeTAD is demonstrated.

786 citations

Journal ArticleDOI
19 Jul 2017-Nature
TL;DR: Observations establish that a molecular uranium complex can promote the stoichiometric transformation of N2 into NH3 or cyanate, and that a flexible, electron-rich, multimetallic, nitride-bridged core unit is a promising starting point for the design of molecular complexes capable of cleaving and functionalizing N2 under mild conditions.
Abstract: Molecular nitrogen (N2) is cheap and widely available, but its unreactive nature is a challenge when attempting to functionalize it under mild conditions with other widely available substrates (such as carbon monoxide, CO) to produce value-added compounds. Biological N2 fixation can do this, but the industrial Haber-Bosch process for ammonia production operates under harsh conditions (450 degrees Celsius and 300 bar), even though both processes are thought to involve multimetallic catalytic sites. And although molecular complexes capable of binding and even reducing N2 under mild conditions are known, with co-operativity between metal centres considered crucial for the N2 reduction step, the multimetallic species involved are usually not well defined, and further transformation of N2-binding complexes to achieve N-H or N-C bond formation is rare. Haber noted, before an iron-based catalyst was adopted for the industrial Haber-Bosch process, that uranium and uranium nitride materials are very effective heterogeneous catalysts for ammonia production from N2. However, few examples of uranium complexes binding N2 are known, and soluble uranium complexes capable of transforming N2 into ammonia or organonitrogen compounds have not yet been identified. Here we report the four-electron reduction of N2 under ambient conditions by a fully characterized complex with two Uiii ions and three K+ centres held together by a nitride group and a flexible metalloligand framework. The addition of H2 and/or protons, or CO to the resulting complex results in the complete cleavage of N2 with concomitant N2 functionalization through N-H or N-C bond-forming reactions. These observations establish that a molecular uranium complex can promote the stoichiometric transformation of N2 into NH3 or cyanate, and that a flexible, electron-rich, multimetallic, nitride-bridged core unit is a promising starting point for the design of molecular complexes capable of cleaving and functionalizing N2 under mild conditions.

199 citations

Journal ArticleDOI
TL;DR: The condensation of multiple building blocks in a ball mill allows molecular cages with a size up to 3.1 nm to be built.
Abstract: The condensation of multiple building blocks in a ball mill allows molecular cages with a size up to 3.1 nm to be built.

163 citations

Journal ArticleDOI
TL;DR: The chiral stationary phase for zinc selectivity has been reported for the first time and the chiral phase for transition mas nmr has also been reported.
Abstract: Keywords: transition mas nmr ; coordination polymers ; magic-angle ; magnetic-resonance ; molecular-dynamics ; spectra ; resolution ; chains ; zinc ; selectivity Reference LCOM-ARTICLE-2005-015doi:10.1002/anie.200500207View record in Web of Science Record created on 2005-11-09, modified on 2017-05-12

162 citations

Journal ArticleDOI
TL;DR: This work reproduced the loss of picolinate and acetylacetonate ancillary ligands in solution by the addition of Brønsted or Lewis acids and advantageously used this degradation reaction for the efficient synthesis of tris-heteroleptic cyclometalated iridium(III) complexes.
Abstract: Investigations of blue phosphorescent organic light emitting diodes (OLEDs) based on [Ir(2-(2,4-difluorophenyl)pyridine)(2)(picolinate)] (FIrPic) have pointed to the cleavage of the picolinate as a possible reason for device instability. We reproduced the loss of picolinate and acetylacetonate ancillary ligands in solution by the addition of Bronsted or Lewis acids. When hydrochloric acid is added to a solution of a [Ir(C(∧)N)(2)(X(∧)O)] complex (C(∧)N = 2-phenylpyridine (ppy) or 2-(2,4-difluorophenyl)pyridine (diFppy) and X(∧)O = picolinate (pic) or acetylacetonate (acac)), the cleavage of the ancillary ligand results in the direct formation of the chloro-bridged iridium(III) dimer [{Ir(C(∧)N)(2)(μ-Cl)}(2)]. When triflic acid or boron trifluoride are used, a source of chloride (here tetrabutylammonium chloride) is added to obtain the same chloro-bridged iridium(III) dimer. Then, we advantageously used this degradation reaction for the efficient synthesis of tris-heteroleptic cyclometalated iridium(III) complexes [Ir(C(∧)N(1))(C(∧)N(2))(L)], a family of cyclometalated complexes otherwise challenging to prepare. We used an iridium(I) complex, [{Ir(COD)(μ-Cl)}(2)], and a stoichiometric amount of two different C(∧)N ligands (C(∧)N(1) = ppy; C(∧)N(2) = diFppy) as starting materials for the swift preparation of the chloro-bridged iridium(III) dimers. After reacting the mixture with acetylacetonate and subsequent purification, the tris-heteroleptic complex [Ir(ppy)(diFppy)(acac)] could be isolated with good yield from the crude containing as well the bis-heteroleptic complexes [Ir(ppy)(2)(acac)] and [Ir(diFppy)(2)(acac)]. Reaction of the tris-heteroleptic acac complex with hydrochloric acid gives pure heteroleptic chloro-bridged iridium dimer [{Ir(ppy)(diFppy)(μ-Cl)}(2)], which can be used as starting material for the preparation of a new tris-heteroleptic iridium(III) complex based on these two C(∧)N ligands. Finally, we use DFT/LR-TDDFT to rationalize the impact of the two different C(∧)N ligands on the observed photophysical and electrochemical properties.

158 citations


Cited by
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Journal ArticleDOI
TL;DR: In this paper, the triple cation perovskite photovoltaics with inorganic cesium were shown to be thermally more stable, contain less phase impurities and are less sensitive to processing conditions.
Abstract: 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.

3,470 citations

Journal ArticleDOI
TL;DR: 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.
Abstract: 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.)

3,242 citations

Journal ArticleDOI
14 Oct 2016-Science
TL;DR: This work shows that the small and oxidation-stable rubidium cation (Rb+) can be embedded into a “cation cascade” to create perovskite materials with excellent material properties and achieved stabilized efficiencies of up to 21.6% on small areas.
Abstract: 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.

3,034 citations

Journal ArticleDOI
TL;DR: This critical review describes the latest developments in the sensitization of near-infrared luminescence, "soft" luminescent materials (liquid crystals, ionic liquids, ionogels), electroluminescentmaterials for organic light emitting diodes, with emphasis on white light generation, and applications in luminecent bio-sensing and bio-imaging based on time-resolved detection and multiphoton excitation.
Abstract: 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).

2,895 citations