Foto personale

Emanuela LIBERTINI

Department of Chemical and Geological Sciences

Tassinari, Francesco; Libertini, Emanuela; Parenti, Francesca; Mucci, Adele ( 2017 ) - Polymers with Alkylsulfanyl Side Chains for Bulk Heterojunction Solar Cells: Toward a Greener Strategy - MACROMOLECULAR CHEMISTRY AND PHYSICS - n. volume 218 - pp. da 1 a 14 ISSN: 1521-3935 [Articolo in rivista (262) - Articolo su rivista]
Abstract

The synthesis and properties of three co-polymers obtained through a Knoevenagel poly-condensation are reported. They are soluble in organic solvents, filmable and solvatochromic. They are characterized through GPC, NMR and UV-visible spectroscopies, CV, and AFM. They display some proneness to form π-stacks, broad absorptions up to about 700 nm, HOMO and LUMO energies that fit those of [60]PCBM. The polymers are incorporated in blends with PCBM within BHJ devices. The best results are found for PSCs obtained from P1 (2.7 % PCE). The insertion of alkylsulfanyl chains improves the photovoltaic performances, with respect to those of alkyl-substituted analogous polymers. The Jsc of the devices are greatly enhanced, supporting the employment of (alkylsulfanyl)thienyl units as base units in photoactive materials.

Parenti, Francesca; Tassinari, Francesco; Libertini, Emanuela; Lanzi, Massimiliano; Mucci, Adele ( 2017 ) - Π‑Stacking Signature in NMR Solution Spectra of Thiophene-Based Conjugated Polymers - ACS OMEGA - n. volume 2 - pp. da 5775 a 5784 ISSN: 2470-1343 [Articolo in rivista (262) - Articolo su rivista]
Abstract

Studies on conjugated polymers seldom report on their NMR characterization in solution. This paper shows how NMR experiments, both 1H NMR and routine 2D NMR spectra, can help in gaining a further insight into the aggregation behavior of conjugated polymers and could be used to flank the more employed solid-state NMR and other spectroscopy and microscopy techniques in the understanding of the aggregation processes. NMR spectroscopy allows distinguishing, within the class of poorly solvatochromic conjugated polymers, those highly prone to form π-stacked aggregates from the ones that have a low tendency toward π-stacking.

Mucci, A.; Parenti, F.; Libertini, E.; Tassinari, F.; Schenetti, L. ( 2016 ) - CONJUGATED POLYMERS FOR PHOTOVOLTAICS: FROM SOLUTION TO SOLID-STATE NMR - XLV National Congress on Magnetic Resonance, book of abstracts - GIDRM Milano ITA) - n. volume unico - pp. da 18 a 18 ISSN: - [Abstract in Atti di convegno (274) - Abstract in Atti di Convegno]
Abstract

Conjugated polymers are widely studied for applications in organic electronics.[1] The structural scenery is varied and the properties of polymers and copolymers can change heavily with the structure. The characterization of organic polymers used in organic electronics, and in particular in polymer solar cells (PSCs), is strongly multidisciplinary. It requires expertise within different branches of chemistry and at the border among chemistry, physics and engineering. Here, the contribution of solution NMR to the study of self-aggregation properties of thiophene based conjugated polymers will be presented. NMR findings on polymers in solution appear to be correlated to morphological properties and solvatochromism. Since one of the most actively investigated application of conjugated polymers is as donors in bulk hetero junction PSCs, also some results obtained with solid-state NMR on polymer/fullerene blends will be reported.

Tassinari, F.; Parenti, F.; Di Nicola, F. P.; Ballarin, B.; Lanzi, M.; Libertini, E.; Mucci, A. ( 2016 ) - Poly(Cyanovinylene Phenylene-Co-Thiophene)s For Polymer Solar Cells - ENERCHEM 1 -Book of Abstracts [Abstract in Atti di convegno (274) - Abstract in Atti di Convegno]
Abstract

We synthetized, using a Knoevenagel polycondensation reaction, three different poly(phenylenecyanovinylene-co-thiophenes) , slightly changing the structure of the thiophene comonomer, to study the effect that these changes can have on the efficiency of photovoltaic devices built using these polymers

Righi, Valeria; Schenetti, Luisa; Maiorana, Antonino; Libertini, Emanuela; Bettelli, Stefania; Reggiani Bonetti, Luca; Mucci, Adele ( 2015 ) - Assessment of freezing effects and diagnostic potential of BioBank healthy and neoplastic breast tissues through HR-MAS NMR spectroscopy - METABOLOMICS - n. volume 11 - pp. da 487 a 498 ISSN: 1573-3882 [Articolo in rivista (262) - Articolo su rivista]
Abstract

HR-MAS NMR spectroscopy was employed to monitor the metabolic profiles of Modena BioBank breast samples over 1 year of freezing at -80 C. The study includes 22 adult female patients living in Modena and its hinterland, who underwent total mastectomy or quadrantectomy in 2011–2012. Variations occur, especially affecting phosphocholine (PC) and choline. This is not a trivial finding, since many studies base the distinction between neoplastic and healthy tissues or the assessment of tumor grade on the analysis of choline metabolites. Despite the changes observed, we established that the diagnostic power of the HR-MAS NMR spectra of frozen samples is preserved, at least as far as the distinction between neoplastic and healthy samples is concerned. Lactate (Lac), PC, phosphoethanolamine (PE), taurine (Tau), myo-inositol (Myo) and glucose (Glc) are biomarkers that can be used to distinguish healthy from neoplastic tissues, whereas some metabolite ratios, such as Lac ? PE ? Tau/Glc ? Myo, seem to have even higher discrimination potential.

Libertini, E.; Morvillo, P.; Mucci, A.; Tassinari, F.; Schenetti, L.; Parenti, F. ( 2015 ) - Synthesis Of Low Band-Gap Conjugated Polymers For Application In Solar Cells - Atti del Convegno - Società Chimica Italiana Roma ITA) - n. volume unico - pp. da 74 a 74 ISBN: 978-88-86208-97-0 ISSN: - [Abstract in Atti di convegno (274) - Abstract in Atti di Convegno]
Abstract

Polymer solar cells are a fascinating low cost alternative to silicon-based solar cells1 thanks to light weight, mechanical flexibility and processability. The polymers suitable for this purpose should possess good filming and absorption properties (absorption coefficients >105 cm-1 and UV–Vis spectrum ideally matching the solar spectrum)2, high hole mobility, and HOMO–LUMO energy levels suitable to be coupled with the acceptor species3. In this presentation the synthesis of three different low band gap copolymers is reported and discussed. The properties of these materials are compared in order to gain an insight on the molecular structure-performance relationship of the final device

Adele Mucci; Francesca Parenti; Emanuela Libertini; Luisa Schenetti ( 2013 ) - Accordo di Collaborazione con ENEA Sintesi e caratterizzazione di nuovi polimeri semiconduttori per celle fotovoltaiche organiche – Responsabile UNIMORE Accordo di Programma Ministero dello Sviluppo Economico - ENEA Area: Produzione di energia elettrica e protezione dell’ambiente Progetto: Energia elettrica da fonte solare – Ricerca su celle fotovoltaiche innovative Obiettivo E: Sviluppo di celle organiche Piano Triennale della Ricerca nell’ambito del Sistema Elettrico Nazionale 2012-2014. [Altro (298) - Partecipazione a progetti di ricerca]
Abstract

La "Ricerca di sistema elettrico" è un programma che prevede un insieme di attività di ricerca e sviluppo finalizzate a ridurre il costo dell'energia elettrica per gli utenti finali, migliorare l'affidabilità del sistema e la qualità del servizio, ridurre l'impatto del sistema elettrico sull'ambiente e sulla salute e consentire l'utilizzo razionale delle risorse energetiche ed assicurare al Paese le condizioni per uno sviluppo sostenibile. All'interno di questo progetto la nostra unità ha avuto il compito di realizzare la sintesi di polimeri semiconduttori a bassa gap da utilizzare come materiali donori in celle fotovoltaiche organiche aventi come materiale attivo una miscela polimero-fullerene.

R. Cagnoli; M. Caselli; E. Libertini; A. Mucci; F. Parenti; G. Ponterini;L. Schenetti ( 2012 ) - Aggregation behaviour of a water-soluble ammonium-functionalizedpolythiophene: Luminescence enhancement induced by bile-acid anions - POLYMER - n. volume 53 - pp. da 403 a 410 ISSN: 0032-3861 [Articolo in rivista (262) - Articolo su rivista]
Abstract

The water-soluble poly{trimethyl-[7-(3-thienylsulfanyl)heptyl]ammonium iodide-co-thiophene} (PTNDMe3) forms aggregates whose size span a large range of values, depending on solvent, concentrationand film formation conditions. Larger aggregates were detected by atomic force microscopy and dynamic light scattering, smaller ones by DOSY NMR, UVevisible and fluorescence. All techniques indicate a reduced aggregation of PTNDMe3 in DMSO relative to water and a marked de-aggregation of PTNDMe3 in water following addition of bile-acid anions such as deoxycholate and ursodeoxycholate.The latter effect shows itself through a very large enhancement of the polymer photoluminescence likely caused by disruption of aggregated non-emissive exciton traps. A tailored combination of electrostaticand hydrophobic interactions between the polymer and the bile-acid anions seems to be necessary to achieve this effect. These observations suggest that this polythiophene might provide a basis for the development of fluorescent sensors suitable for the detection of medium-sized amphiphilic biomolecules.

L. Preti; R. Cagnoli; F. Parenti; M. Lanzi; E. Libertini; D. Pinetti; l. Schenetti; A. Mucci ( 2010 ) - Octithiophenes via One-Pot Oxidative Coupling of 4-(ω-Functionalized Alkylsulfanyl)-2,2′-Bithiophenes - SYNTHESIS - n. volume 2010 - pp. da 1659 a 1665 ISSN: 0039-7881 [Articolo in rivista (262) - Articolo su rivista]
Abstract

The oxidative coupling reaction with FeCl3 on nitrile, methyl ester and amino functionalized 4-(alkylsulfanyl)-2,2’-bitiophenes afforded symmetric octithiophenes (OTs). These new OTs have solvatochromic properties similar to those reported for poly(ω-functionalized alkylsulfanyl)thiophenes and have a potential use in optoelectronic devices. The carboxy (obtained through hydrolysis from nitrile and methyl ester functionalized OTs) and the amino functionalized OTs are also water soluble as salts. From this and our previous results, the oxidative coupling with FeCl3 can be proposed as a general method for the synthesis of OTs when the starting materials are 4-(alkylsulfanyl)-, 4-(ω-functionalized alkylsulfanyl)-, and 4-alkylsulfanyl-4’-halo-2,2’-bithiophenes.

R. Cagnoli; E. Libertini;A. Mucci; F. Parenti; D. Pinetti; L. Preti; L. Schenetti ( 2008 ) - Aggregation Properties of Aminoalkylsulfanyl Polythiophenes - - ATTI- 32° Convegno Nazionale della Divisione di Chimica Organica della SCI - Società Chimica Italiana - Divisione di Chimica Organica Taormina ITA) - n. volume unico [Abstract in Atti di convegno (274) - Abstract in Atti di Convegno]
Abstract

The aggregation properties of an aminoalkylsulfanyl polythiophenes cayying a tromethylammonium group were characterized through a combined AFM, DOSY NMR and DLS study.

F. Parenti; R. Cagnoli; M. Caselli; E. Libertini; A. Mucci; D. Pinetti; G. Ponterini; L. Preti; L. Schenetti ( 2008 ) - "Aminoalkylsulfanyl substituted polithiophene: an aggregation study" - Workshop on Nanomaterials Production, Characterization and Industrial Applications - . . ITA) - n. volume . [Abstract in Atti di convegno (274) - Abstract in Atti di Convegno]
Abstract

The aggregation properties of poly{trimethyl-[7-(3-thienylsulfanyl)heptyl]ammonium iodide-co-thiophene} (PTN+Me3) (Fig.1) were investigated through NMR, AFM, light scattering and fluorescence spectroscopy.

F. Parenti; D. Pinetti; G. Ponterini; L. Preti; L. Schenetti;R. Cagnoli; M. Caselli; E. Libertini; A. Mucci ( 2008 ) - Aminoalkylsulfanyl Substituted Polythiophene: an Aggregation Study - Workshop on Nanomaterials Production, Characterization ans Industrial Applications - Extended abstract - AIDIC Milano ITA) - n. volume unico - pp. da 25 a 25 ISBN: non disponibile ISSN: - [Contributo in Atti di convegno (273) - Relazione in Atti di Convegno]
Abstract

The aggregation behaviour of poly{trimethyl-[7-(3-thienylsulfanyl)heptyl]ammonium iodide-co-thiophene} (PTN+Me3) was investigated through NMR, atomic force microscopy (AFM), dynamic light scattering (DLS), UV-Vis and fluorescence spectroscopy. The interaction with sodium ursodesoxycholate (NaUDC) causes a marked enhancement of fluorescence emission.

R. CAGNOLI; M. LANZI; E. LIBERTINI; A. MUCCI; L. PAGANIN; F. PARENTI; L. PRETI; L. SCHENETTI ( 2008 ) - Organic- and Water-Soluble Aminoalkylsulfanyl Polythiophenes - MACROMOLECULES - n. volume 41 - pp. da 3785 a 3792 ISSN: 0024-9297 [Articolo in rivista (262) - Articolo su rivista]
Abstract

Six new aminoalkylsulfanyl polythiophenes (PTs), namely PTNHBoc, PTNMeBoc, PTNH2,PTNHMe, PTNMe2, and PTN+Me3, were synthesized. Four of them were obtained through Stille coupling, whereasPTNH2 and PTNHMe were obtained through deprotection via N-Boc precursors. The solubility changes goingfrom the protected amines to the quaternary ammonium salt. All the polymers are soluble in DMSO and DMF.PTNHBoc and PTNMeBoc are also soluble in CHCl3, CH2Cl2, THF, and DMPU; PTNH2 and PTNHMe aresoluble in CH3OH, whereas PTNMe2 and PTN+Me3 are soluble both in CH3OH and in H2O. These PTs show atendency toward microaggregation in solution that does not represent an obstacle to their solubility. NMR, UV-vis,and XRD results prove that they are able to reach very high conjugation lengths and ordered conformations, notonly in the solid state but also in solutions of good solvents.

F. Ghelfi; CV Stevens; I. Laureyn; E. Van Meenen; TM Rogge; L. De Buyck; K V Nikitin; R. Grandi; E. Libertini; UM Pagnoni; L. Schenetti ( 2003 ) - Synthesis of 5-methoxylated 3-pyrrolin-2-one via the rearrangement of chlorinated pyrrolidin-2-ones - TETRAHEDRON - n. volume 59 - pp. da 1147 a 1157 ISSN: 0040-4020 [Articolo in rivista (262) - Articolo su rivista]
Abstract

The reaction of N-substituted 4-methyl-2-pyrrolidinones or 4-diethoxyphosphoryl analogues, carrying at least two chlorine atoms between the C(3) and C(6) carbons, with alkaline methoxide in methanol afforded the corresponding 5-methoxylated 3-pyrrolin-2-ones, useful adducts for the preparation of agrochemicals or medicinal compounds. (C) 2003 Elsevier Science Ltd. All rights reserved.

M.E. CASARINI; F. GHELFI; E. LIBERTINI; U.M. PAGNONI; A.F. PARSONS ( 2002 ) - 1,2-reduction of alpha,beta-unsaturated hydrazones using dimethylamine-borane/p-toluenesulfonic acid: an easy route to allyl hydrazines - TETRAHEDRON - n. volume 58 - pp. da 7925 a 7932 ISSN: 0040-4020 [Articolo in rivista (262) - Articolo su rivista]
Abstract

alpha,beta-Unsaturated hydrazones can be easily converted into N-allyl hydrazines by reaction with dimethylamine-borane/p-toluenesulfonic acid under mild reaction conditions. The reduction works well for N'-allyhydrazides but N'-allyl-N,N-dimethylhydrazines are rapidly reoxidised by air and so need to be manipulated under an inert atmosphere prior to M-acylation. Competitive conjugate reduction can also be observed and the regioselectivity of the dimethylamine-borane attack is determined by steric and/or electronic factors. The procedure is also effective for the C=N reduction of unconjugated hydrazones. (C) 2002 Elsevier Science Ltd. All rights reserved.

F. BELLESIA; L. DE BUYCK; M.V. COLUCCI; F. GHELFI; I. LAUREYN; E. LIBERTINI; A. MUCCI; U.M. PAGNONI; A. PINETTI; T.M. ROGGE; C.V. STEVENS ( 2001 ) - Unusual access to 5-methoxy or 5,5-dimethoxy-4-methyl-3-pyrrolin-2-ones from chlorinated 4-methyl-pyrrolidin-2-ones - Elsevier Science Limited:Oxford Fulfillment Center, PO Box 800, Kidlington Oxford OX5 1DX United Kingdom:011 44 1865 843000, 011 44 1865 843699, EMAIL: asianfo@elsevier.com, tcb@elsevier.co.UK, INTERNET: http://www.elsevier.com, http://www.elsevier.com/locate/shpsa/, Fax: 011 44 1865 843010 ) - TETRAHEDRON LETTERS - n. volume 42 - pp. da 4573 a 4575 ISSN: 0040-4039 [Articolo in rivista (262) - Articolo su rivista]
Abstract

The reaction of N-substituted 4-methyl-2-pyrrolidinones, carrying not less than two chlorine atoms on the C(3) and C(6) carbons afforded with alkaline methoxide in methanol, under mild conditions, the corresponding 5-methoxy or 5,5-dimethoxy-4-methyl-3-pyrrolin-2-ones in satisfactory yields.

F. Bellesia; L. De Buyck; F. Ghelfi; E. Libertini; UM Pagnoni; F. Roncaglia ( 2000 ) - 2,2-dichlorination of aldehydes with the 2,6-lutidine center dot HCl/Cl-2/CH2Cl2 system: An environmentally benign process suitable for scale up - TETRAHEDRON - n. volume 56 - pp. da 7507 a 7511 ISSN: 0040-4020 [Articolo in rivista (262) - Articolo su rivista]
Abstract

An effective and environmentally benign preparation of 2,2-dichloroaldehydes has been achieved by chlorination of aldehydes with Cl-2(g) in CH2Cl2, using 2,6-lutidine hydrochloride as recoverable catalyst. Remarkable qualities of the process are: easy work up, high purity products, HCl as the only 'waste' stream and inherent bias to the scale up. (C) 2000 Elsevier Science Ltd. All rights reserved.

F. Ghelfi; G. Ghirardini; E. Libertini; L. Forti; U.M. Pagnoni ( 1999 ) - Easy approach to 3-benzylimino-2-pyrrolidinones from 3-chloro-4-chloromethyl-2-pyrrolidinones - TETRAHEDRON LETTERS - n. volume 40 - pp. da 8595 a 8597 ISSN: 0040-4039 [Articolo in rivista (262) - Articolo su rivista]
Abstract

3-Benzylimino-2-pyrrolidinones can be prepared in good yield by heating 3-chloro-4-chloromethyl-2-pyrrolidinones, benzylamine and NaI in THF at 80 degrees C. An endo-dehydrohalogenation followed by a SN2' substitution on the intermediate allyl chloride, and finally a shift of the exo-double bond to Delta(3) with attendant tautomerization, appears to be the most probable reaction mechanism. (C) 1999 Elsevier Science Ltd. All rights reserved.

F. Bellesia; L. Forti; F. Ghelfi; G. Ghirardini; E. Libertini; U.M. Pagnoni; A. Pinetti; N. Prochilo ( 1999 ) - Rearrangement of N-allyl-alpha,alpha-dichloroamides, beta- or gamma-functionalized, to substituted analogues of the gamma-aminobutyric acid (GABA) - SYNTHETIC COMMUNICATIONS - n. volume 29 - pp. da 3739 a 3748 ISSN: 0039-7911 [Articolo in rivista (262) - Articolo su rivista]
Abstract

The rearrangement of gamma-chloro, beta-hydroxy or beta-vinyl N-allyl-N-benzyl-alpha,alpha-dichlorocarboxyamides to gamma-aminobutyric acid analogues is efficiently promoted by CuCl\N,N,N',N'-tetramethylethylendiamine. With the beta-vinyl functionalization a tandem radical-radical reaction, yielding 3-aza-2-oxo-bicyclo[3,3,0]octane adducts, is also observed.

F. Ghelfi; F. Bellesia; L. Forti; G. Ghirardini; R. Grandi; E. Libertini; M.C. Montemaggi; U.M. Pagnoni; A. Pinetti; L. De Buyck; A.F. Parson ( 1999 ) - The influence of benzylic protection and allylic substituents on the CuCl-TMEDA catalyzed rearrangement of N-allyl-N-benzyl-2,2-dihaloamides to gamma-lactams. Application to the stereoselective synthesis of pilolactam. - TETRAHEDRON - n. volume 55 - pp. da 5839 a 5852 ISSN: 0040-4020 [Articolo in rivista (262) - Articolo su rivista]
Abstract

A number of N-benzylic protecting groups and allylic substituents have been investigated for the rearrangement, promoted by CuCl-TMEDA, of N-allyl-2,2-dihaloamides to 3,4-disubstituted gamma-lactams. An appreciable chiral induction was observed at the C-4 site when alpha-phenylethylamine was used as a chiral protecting group, while an unexpected Diels-Alder reaction occurred when using a 2-furyl-methyl protection. This rearrangement has been applied to the synthesis of pilolactam, a drug with muscarinic activity. (C) 1999 Elsevier Science Ltd. All rights reserved.

F. Bellesia; L. Forti; E. Gallini; F. Ghelfi; E. Libertini; U.M. Pagnoni ( 1998 ) - Telechelic oligomers by halogen atom transfer radical addition - TETRAHEDRON - n. volume 54 - pp. da 7849 a 7856 ISSN: 0040-4020 [Articolo in rivista (262) - Articolo su rivista]
Abstract

Monodispersed telechelic oligomers have been efficiently prepared by Fe-0-FeCl3 promoted halogen atom transfer radical of functional telogens and taxogens, (C) 1998 Elsevier Science Ltd. All rights reserved.

L. Forti; F. Ghelfi; E. Libertini; U.M. Pagnoni; E. Soragni ( 1997 ) - Halogen atom transfer radical addition of alpha-polychloroesters to olefins promoted by Fe-0 filings - TETRAHEDRON - n. volume 53 - pp. da 17761 a 17768 ISSN: 0040-4020 [Articolo in rivista (262) - Articolo su rivista]
Abstract

The Kharasch addition of methyl 2,2-dichlorocarboxylates or trichloro acetic acid derivatives to alkenes, affording the corresponding 1:1 adducts, is promoted by the iron filings/N,N-dimethylformamide system.

L. Forti; F. Ghelfi; R. Grandi; E. Libertini; U.M. Pagnoni ( 1996 ) - N-(2-hydroxyalkyl)-2,2-dihaloamides by amino-de-alkoxylation of methyl 2,2-dihalocarboxylates - SYNTHETIC COMMUNICATIONS - n. volume 26 - pp. da 3517 a 3526 ISSN: 0039-7911 [Articolo in rivista (262) - Articolo su rivista]
Abstract

The chemoselective N-acylation of 2-amino alcohols with methyl 2,2-dichloro carboxylates occurs smoothly and in excellent yields.

M. Benincasa; L. Forti; F. Ghelfi; E. Libertini; U.M. Pagnoni ( 1996 ) - Zinc promoted addition of methyl 2,2-dihalocarboxylates to carbonyl compounds - SYNTHETIC COMMUNICATIONS - n. volume 26 - pp. da 4113 a 4122 ISSN: 0039-7911 [Articolo in rivista (262) - Articolo su rivista]
Abstract

Methyl 2,2-dihalocarboxylates add easily to carbonyl compounds in fair to good yields through the intermediate formation of 2-haloester enolates; the reaction is promoted by zinc, following a ''Barbier'' type procedure.