Mauro Sassi

Multichromophoric electrochromic polymers: Colour tuning of conjugated polymers through the side chain functionalization approach

Organic electrochromic materials have gained constantly increasing interest over the years with respect to their inorganic counterpart due to essentially two distinctive characteristics: their processability through solution based low cost processes and their wide colour palette. Such characteristic features enabled their application in displays, smart windows, electronic paper and ophthalmic lenses. Alongside the established concept of donor-acceptor polymers, side chain functionalized multichromophoric polymers are gaining attention as a highly performing and synthetically feasible alternative, particularly relevant to applications requiring a complete colourlessness in one of the accessible redox states of the material. The primary aim of the present article is to review all the results involving the tuning of the native electrochromic properties of simple conjugated polymers through the introduction of a discrete electrochromic molecule as a side chain substituent.

High Stokes shift perylene dyes for luminescent solar concentrators

Highly efficient plastic based single layer Luminescent Solar Concentrators (LSCs) require the design of luminophores having complete spectral separation between absorption and emission spectra (large Stokes shift). We describe the design, synthesis and characterization of a new perylene dye possessing Stokes shift as high as 300 meV, fluorescent quantum yield in the LSC slab of 70% and high chemical and photochemical stability.

Panchromatic Cross-Substituted Squaraines for Dye-Sensitized Solar Cell Applications

Keywords: light harvesting ; photochromism ; sensitizers ; solar cells ; squaraines ; Organic Sensitizers ; Highly Efficient Reference EPFL-ARTICLE-159583doi:10.1002/cssc.200900077View record in Web of Science Record created on 2010-11-30, modified on 2017-05-12

Gray to Colorless Switching, Crosslinked Electrochromic Polymers with Outstanding Stability and Transmissivity From Naphthalenediimmide‐Functionalized EDOT

The design, synthesis, polymerization and full electrochemical and spectroelectrochemical characterization of a new naphtalendiimide-functionalized PEDOT cross-linked electrochromic material is reported. The polymer shows exceptionally high redox reversibility, almost complete colorlessness in the bleached state and a gray color in the reduced state.

Stokes shift/emission efficiency trade-off in donor–acceptor perylenemonoimides for luminescent solar concentrators

Perylenediimides (PDIs) are among the best performing organic luminescent materials, both in terms of emission efficiency and chemical and photochemical stability because of their rigid, symmetric and planar structure; however, they exhibit very small Stokes shifts. The sizeable reabsorption of the emitted light limits the performances of perylenediimides in imaging applications and luminescent solar concentrators. Perylenemonoimides (PMIs) having an electron donating substituent in one of the free peri positions feature larger Stokes shift values while retaining high chemical stability. The selection of the most appropriate donor, both in terms of electron donating capability and steric demand, boosts emission efficiency and limits reabsorption losses. The synthesis, optical spectroscopy, molecular orbital computations, UPS, electrochemical, spectroelectrochemical, and multinuclear NMR investigation of a series of PMI derivatives functionalized with donors having different electronic characteristics and steric demands are discussed. Results are relevant for the fabrication of single layer plastic luminescent solar concentrators (LSC).

Perfluorinated nitrosopyrazolone-based erbium chelates: a new efficient solution processable NIR emitter

We show the design and synthesis of new perfluorinated nitrosopyrazolone-based ligands and the original method employed for their complexation of erbium ions in the presence of the co-ligand perfluorotriphenylphosphine oxide; the resulting chelate is non-hygroscopic, solution processable and possesses a NIR emission with lifetimes as long as 16 micros.

Straightforward fabrication of stable white LEDs by embedding of inorganic UV-LEDs into bulk polymerized polymethyl-methacrylate doped with organic dyes.

Stable white-emitting down-converted LEDs are straightforwardly prepared by bulk polymerization of an organic dye doped polymethyl-methacrylate (PMMA) shell directly on top of a highly efficient commercial blue-emitting InGaN LED. Our optimized polymerization procedure allows for extending the form factor of achievable luminescence converter (LUCO) material beyond the conventional thin film form and to directly produce devices with light bulb design. The selected organic dyes, the blue-emitting Coumarin 30 and a red-emitting diketopyrrolopyrrole derivative, exhibit high compatibility with the free radical polymerization reaction of the PMMA matrix and ensure high stability of the final hybrid device. The control of both the thickness of the PMMA shell and the concentration of the dopant dyes allow for fine tuning of the emission color of the LUCO LED and to obtain white light with CIE chromatic coordinates x = 0.32 and y = 0.33, with rendering index as high as 80. This simple and versatile procedure is not dye-exclusive and is therefore extendable to other molecular systems for color-tunable efficient solid-state lighting sources.

Suzuki-Miyaura Micellar Cross-Coupling in Water, at Room Temperature, and under Aerobic Atmosphere.

Recently, oxygen-equilibrated water solutions of Kolliphor EL, a well-known surfactant, have been seen to form nanomicelles with oxygen-free cores. This has prompted the successful testing of the core environment as a green medium for palladium-catalyzed Suzuki-Miyaura cross couplings. The versatility of these conditions is endorsed by several examples, including the synthesis of relevant molecular semiconductors. The reaction medium can also be recycled, opening the way for an extremely easy and green chemistry compliant methodology.

Unraveling Triplet Excitons Photophysics in Hyper-Cross-Linked Polymeric Nanoparticles: Toward the Next Generation of Solid-State Upconverting Materials

The technological application of sensitized upconversion based on triplet-triplet annihilation (TTA) requires the transition from systems operating in liquid solutions to solid-state materials. Here, we demonstrate that the high upconversion efficiency reported in hyper-cross-linked nanoparticles does not originate from residual mobility of the embedded dyes as it happens in soft hosts. The hyper-reticulation from one side blocks the dyes in fixed positions, but on the other one, it suppresses the nonradiative spontaneous decay of the triplet excitons, reducing intramolecular relaxations. TTA is thus enabled by an unprecedented extension of the triplet lifetime, which grants long excitons diffusion lengths by hopping among the dye framework and gives rise to high upconversion yield without any molecular displacement. This finding paves the way for the design of a new class of upconverting materials, which in principle can operate at excitation intensities even lower than those requested in liquid or in rubber hosts.

Near-infrared roll-off-free electroluminescence from highly stable diketopyrrolopyrrole light emitting diodes.

Organic light emitting diodes (OLEDs) operating in the near-infrared spectral region are gaining growing relevance for emerging photonic technologies, such as lab-on-chip platforms for medical diagnostics, flexible self-medicated pads for photodynamic therapy, night vision and plastic-based telecommunications. The achievement of efficient near-infrared electroluminescence from solution-processed OLEDs is, however, an open challenge due to the low photoluminescence efficiency of most narrow-energy-gap organic emitters. Diketopyrrolopyrrole-boron complexes are promising candidates to overcome this limitation as they feature extremely high photoluminescence quantum yield in the near-infrared region and high chemical stability. Here, by incorporating suitably functionalized diketopyrrolopyrrole derivatives emitting at ~760 nm in an active matrix of poly(9,9-dioctylfluorene-alt-benzothiadiazole) and without using complex light out-coupling or encapsulation strategies, we obtain all-solution-processed NIR-OLEDs with external quantum efficiency as high as 0.5%. Importantly, our test-bed devices show no efficiency roll-off even for high current densities and high operational stability, retaining over 50% of the initial radiant emittance for over 50 hours of continuous operation at 10 mA/cm2, which emphasizes the great applicative potential of the proposed strategy.