ERC FUNDED PROJECTS

The use of renewable feedstocks by the chemical industry is fundamental due to both the depletion of fossil resources and the increasing pressure of environmental concerns. Biomass can act as a sustainable source of organic industrial chemicals; however, the establishment of a renewable chemical industry that is economically competitive with the present oil-based one requires the development of new processes to convert biomass-derived compounds into useful industrial materials following the principles of green chemistry. To achieve these goals, developments in several fields including heterogeneous catalysis are needed. One of the ways to accelerate the discovery of new potentially active, selective and stable catalysts is the massive use of computational chemistry. Recent advances have demonstrated that Density Functional Theory coupled to ab initio thermodynamics, transition state theory and microkinetic analysis can provide a full view of the catalytic phenomena. The aim of the present project is thus to employ these well-tested computational techniques to the development of a theoretical framework that can accelerate the identification of new catalysts for the conversion of biomass derived target compounds into useful chemicals. Since compared to petroleum-based materials-biomass derived ones are multifuncionalized, the search for new catalytic materials and processes has a strong requirement in the selectivity of the chemical transformations. The main challenges in the project are related to the high functionalization of the molecules, their liquid nature and the large number of potentially competitive reaction paths. The requirements of specificity and selectivity in the chemical transformations while keeping a reasonably flexible framework constitute a major objective. The work will be divided in three main work packages, one devoted to the properties of small molecules or fragments containing a single functional group; the second addresses competition in multiple functionalized molecules; and third is dedicated to the specific transformations of two molecules that have already been identified as potential platform generators. The goal is to identify suitable candidates that could be synthetized and tested in the Institute facilities.

1 496 200 €

Start date: 2010-10-01, End date: 2015-09-30

Molecular sciences offer unparalleled opportunities for the development of tailor-made materials. By chemical design, molecules with the desired features can be prepared and incorporated into hybrid systems to yield molecule-based materials with novel chemical and/or physical properties. The CHEMCOMP project aims to develop new hybrid materials targeting the study of new physical phenomena that have already been theoretically predicted or experimentally hinted. The main goals will be: i) Molecules with memory: Memory effect at the molecular scale is of great interest because it represents the size limit in the miniaturization of information storage media. My goal will be to develop spin crossover molecules with bulk-like hysteretic behavior where the switching between the low spin ground state and the high spin metastable state can be controlled through external stimuli. ii) Bistable organic conductors: Bistable molecules could also be embedded into hybrid organic conductors to induce structural phase transitions. This strategy will allow for the transport properties to be controlled through external stimuli in unprecedented switchable conducting media. iii) Hybrid conducting magnets: Combination of magnetism and electrical conductivity has given rise to new phenomena in the past, such as spin glass behavior or giant magnetoresistance. We propose to incorporate Single Molecule Magnets (molecules with magnet-like behavior) into organic (super)conductors to understand and optimize the synergy between these two physical properties. iv) Chiral magnets and conductors: New phenomena is expected to appear in optically active media. Experimental evidence for the so-called MagnetoChiral Dichroism has already been found. Electrical Magnetochiral Anisotropy has been predicted. I will develop systematic strategies for the preparation of hybrid chiral materials to understand and optimize the synergy between chirality and bulk physical properties.

1 940 396 €

Start date: 2012-01-01, End date: 2016-12-31

"Boronic esters are versatile synthetic intermediates for the preparation of a wide range of organic molecules. The recent approval of the anti-cancer agent Velcade, the first boronic acid containing drug commercialized, further confirms the status of boronic acid derivatives as an important class of compounds in chemistry and medicine. This proposal aims to develop three new unconventional approaches for the synthesis of boronic esters. The first one is based on the use of copper (low price and low toxicity) to promote unknown borylation reactions. Our method is an important step forward in that it proceeds using catalytic quantities of copper and allows the formation of a C-B bond along with a C-C or a C-N bond in a single catalytic cycle. Additionally, a copper-catalyzed borylation reaction is proposed as the key tool to solve the total synthesis of nigricanoside A, a potent antimitotic agent. The total synthesis of this natural product could have an impact in cancer research similar to that found for taxol or epothilones. The second approach deals with the development of borylation reactions under metal-free conditions. I propose to use bifunctional catalysts to promote the dual activation of B-B bonds and suitable electrophiles. This approach constitutes an unconventional way to synthesize boronic esters and has no precedent in the literature. Finally, the third section of this proposal branches into riskier territory. I propose to use Lewis-base/diboron adducts to generate organoboryl radicals. If successful, the potential impact will be very high and will certainly open unexplored ways in boron chemistry. The copper-catalyzed, metal-free, and radical approaches proceed by mechanistically distinct pathways and can give rise to complementary reactivity and selectivity partners. New findings in these areas would represent a significant step in the industrial and academic synthesis of boronic esters."

1 495 200 €

Start date: 2014-02-01, End date: 2019-01-31

Organic electronic devices, such as organic field-effect transistors (OFETs), are raising an increasing interest for their potential in large area coverage and low cost applications. Also, the use of single molecules as active electronic components offers great prospects for the miniaturization of devices and for their compatibility with biological systems. Within this framework, e-GAMES goals are: 1) Molecular logic gates for the storage and transmission of magnetic and optical information and for locally controlling surface wettability. The two huge limitations that hinder the application of molecules in logic gates are: i) Fabrication of devices on a solid support, ii) Concatenation of logic gates. I plan to overcome these drawbacks employing self-assembled monolayers of bistable electroactive molecules. These systems could also be used in the fabrication of surfaces with tunable wettability properties, of high interest in microfluidics and for biosensors. 2) Ambipolar organic field-effect transistors with donor-acceptor systems and their exploitation in light, temperature or pressure sensors, and/or memory devices. Intramolecular electron transfer in organic semiconductors designed for preparing ambipolar OFETs will be explored for the first time. This phenomenon will be exploited for the fabrication of light, pressure or temperature stimuli-responsive OFETs bringing innovative perspectives to the field. 3) Organic/inorganic hybrid devices based on field-effect transistors for sensing environmentally hazardous carbon nanoparticles. Carbon-based nanoparticles are being increasingly used in many applications despite their recognized toxicity. The grounds for the development of a new generation of nanotechnological low-cost and selective sensors based on transistors functionalized with organic sensing molecular monolayers for the detection of such materials will be developed, contributing towards the improvement of citizens’ safety and environmental preservation.

1 499 675 €

Start date: 2012-12-01, End date: 2018-09-30