Research

Research

Synthesis

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The principal goal in ILs chemistry is to synthesize low-cost and low-toxicity ionic compounds having specific properties and a melting point near (or below) room temperature to use as solvents, solvent-catalysts or as materials by adsorption on proper supports or through polymerization processes.

In this regard, our research group is involved in design and synthesis of new ILs, to apply as solvents for specific chemical processes or as principal components or additives for the development of smart-materials and electrical devices, possibly starting from cheap chemicals arising from renewable resources.

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Properties

A relevant part of the research work performed in our laboratories is focused on studying the physico-chemical properties of several classes of ionic liquids, with the goal of connecting macro- (i.e. viscosity and density) and microscopic properties (intrinsic interaction ability of single ionic constituents) to the chemical structure of these systems, taking into account both static and dynamic effects.

To this pourpose physical, transport and electrochemical properties (melting points, phase transitions, glass transition temperature, ionic conductivity, viscosity, density, diffusion coefficients, etc) are measured on pure ILs or ionic mixtures as a function of temperature.

Moreover, spectroscopic and spectrometric measurements (UV, NMR, ESI-MS) are generally performed to evaluate the intermolecular interactions, dynamics, solvation and transport properties.

Kinetic and thermodynamic study of selected reactions are also performed to obtain quantitative information on the solvent properties of ILs.

Finally, FT-IR microscopy is used for the chemical identification of particles and smallest contaminations and the analysis of the distribution of a multitude of different components in complex (bio)materials synthesized in ILs or treated with ILs. These data are used to design and synthesize optimized ILs for specific applications.

Theory - Why theoretical chemistry?

Modeling of solvent effect of molecular liquids has an extensive background; however, the modeling of IL systems is still in its infancy. Recently, we have shown that both the liquid structure and solvation properties of imidazolium based ILs are well reproduced in the framework of RISM integral equation theory. Such approach allows to obtain the liquid structure and the spatial distribution of a ionic solvent around a solute with a very reduced computational cost (minutes) if compared to the one required for molecular dynamics or Monte Carlo simulations (weeks). In this moment, RISM approach is applied to understand the solvation processes of stable compounds and short lived species (intermediates and transition states) in model ionic liquids and how they might differ from the same processes carried out in conventional molecular solvents.

The large unpredictability of ionic liquids properties as solvents, as catalysts, as materials deserve a multidisciplinary approach.

For this reason we combine chemical evidences as reactivity and selectivity and physico-chemical measurements with computational studies.

To explicate the solvent effects of ionic liquids on organic reactivity we use ab-initio calculation on clusters constituted by the reaction actors and one or more ions. This supermolecular approach can explicate specific ion-substrate interactions that are fondamental to understand chemical reactivity in ionic liquids.

Papers

Chiappe, C., Sanzone, A., Mendola, D., Castiglione, F., Famulari, A., Raos, G., Mele, A.Pyrazolium- versus imidazolium-based ionic liquids: Structure, dynamics and physicochemical properties (2013) Journal of Physical Chemistry B, 117 (2), pp. 668-676.

Chiappe, C., Pomelli, C.S.Computational studies on organic reactivity in ionic liquids(2013) Physical Chemistry Chemical Physics, 15 (2), pp. 412-423.

Chiappe, C., Rajamani, S., D’Andrea, F.A dramatic effect of the ionic liquid structure in esterification reactions in protic ionic media(2013) Green Chemistry, 15 (1), pp. 137-143.

D’Arrigo, P., Cerioli, L., Chiappe, C., Panzeri, W., Tessaro, D., Mele, A.Improvements in the enzymatic synthesis of phosphatidylserine employing ionic liquids(2012) Journal of Molecular Catalysis B: Enzymatic, 84, pp. 132-135.

Cerda-Monje, A., Aizman, A., Tapia, R.A., Chiappe, C., Contreras, R.Solvent effects in ionic liquids: Empirical linear energy-density relationships(2012) Physical Chemistry Chemical Physics, 14 (28), pp. 10041-10049.

Pomelli, C.S., Chiappe, C., Lapi, A.Accelerating effect of imidazolium ionic liquids on the singlet oxygen promoted oxidation of thioethers: A theoretical study(2012) Journal of Photochemistry and Photobiology A: Chemistry, 240, pp. 59-65.

Banfi, L., Basso, A., Chiappe, C., De Moliner, F., Riva, R., Sonaglia, L.Development of a stereoselective Ugi reaction starting from an oxanorbornene β-amino acid derivative(2012) Organic and Biomolecular Chemistry, 10 (19), pp. 3819-3829.

Caporali, S., Chiappe, C., Ghilardi, T., Pomelli, C.S., Pinzino, C.Coordination environment of highly concentrated solutions of Cu II in ionic liquids through a multidisciplinary approach(2012) ChemPhysChem, 13 (7), pp. 1885-1892.

Chiappe, C., Pomelli, C.S., Bardi, U., Caporali, S.Interface properties of ionic liquids containing metal ions: Features and potentialities(2012) Physical Chemistry Chemical Physics, 14 (15), pp. 5045-5051.

Chiappe, C., Rajamani, S.Synthesis of glycerol carbonate from glycerol and dimethyl carbonate in basic ionic liquids(2012) Pure and Applied Chemistry, 84 (3), pp. 755-762.

Chiappe, C., Pomelli, C.S.The first solvation shell of Reichardt’s dye in ionic liquids: A semiempirical study(2012) Theoretical Chemistry Accounts, 131 (3), pp. 1-7.

Pucci, A., Liuzzo, V., Melai, B., Pomelli, C.S., Chiappe, C.Polymerizable ionic liquids for the preparation of polystyrene/clay composites(2012) Polymer International, 61 (3), pp. 426-433.

Bellina, F., Chiappe, C., Lessi, M.Synthesis and properties of trialkyl(2,3-dihydroxypropyl)phosphonium salts, a new class of hydrophilic and hydrophobic glyceryl-functionalized ILs(2012) Green Chemistry, 14 (1), pp. 148-155.

Bruzzone, S., Chiappe, C., Focardi, S.E., Pretti, C., Renzi, M.Theoretical descriptor for the correlation of aquatic toxicity of ionic liquids by quantitative structure-toxicity relationships(2011) Chemical Engineering Journal, 175 (1), pp. 17-23.

Fukuhara, G., Okazaki, T., Lessi, M., Nishijima, M., Yang, C., Mori, T., Mele, A., Bellina, F., Chiappe, C., Inoue, Y.Chiral ionic liquid-mediated photochirogenesis. Enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid(2011) Organic and Biomolecular Chemistry, 9 (20), pp. 7105-7112.

Giray, E.S., Chiappe, C., Tunali, Z., Rajamani, S.Effect of several ionic liquids on the synthesis of 1,3-diphenyl-3- (phenylamino)propan-1-one in supercritical carbondioxide(2011) RSC Advances, 1 (5), pp. 761-764.

Chiappe, C., Rajamani, S.Structural effects on the physico-chemical and catalytic properties of acidic ionic liquids: An overview(2011) European Journal of Organic Chemistry, (28), pp. 5517-5539.

Chiappe, C., Pomelli, C.S., Rajamani, S.Influence of structural variations in cationic and anionic moieties on the polarity of ionic liquids(2011) Journal of Physical Chemistry B, 115 (31), pp. 9653-9661.

Chiappe, C., Sanzone, A.Using the chemical tunability of ionic liquids to increase sustainability in the electrophilic bromination of unsaturated compounds(2011) Synthesis, (15), pp. 2392-2396.

Francesco, F.D., Calisi, N., Creatini, M., Melai, B., Salvo, P., Chiappe, C.Water sorption by anhydrous ionic liquids(2011) Green Chemistry, 13 (7), pp. 1712-1717.

Chiappe, C., Sanzone, A., Dyson, P.J.Styrene oxidation by hydrogen peroxide in ionic liquids: The role of the solvent on the competition between two Pd-catalyzed processes, oxidation and dimerization(2011) Green Chemistry, 13 (6), pp. 1437-1441.

Pretti, C., Renzi, M., Ettore Focardi, S., Giovani, A., Monni, G., Melai, B., Rajamani, S., Chiappe, C.Acute toxicity and biodegradability of N-alkyl-N-methylmorpholinium and N-alkyl-DABCO based ionic liquids(2011) Ecotoxicology and Environmental Safety, 74 (4), pp. 748-753.

Marra, A., Chiappe, C., Mele, A.Sugar-derived ionic liquids(2011) Chimia, 65 (1-2), pp. 76-80.

Baciocchi, E., Chiappe, C., Fasciani, C., Lanzalunga, O., Lapi, A.Reaction of singlet oxygen with thioanisole in ionic liquid-acetonitrile binary mixtures(2010) Organic Letters, 12 (22), pp. 5116-5119.

Chiappe, C., Malvaldi, M.Highly concentrated “solutions” of metal cations in ionic liquids: Current status and future challenges(2010) Physical Chemistry Chemical Physics, 12 (37), pp. 11191-11196.

Chiappe, C., Marra, A., Mele, A.Synthesis and applications of ionic liquids derived from natural sugars(2010) Topics in Current Chemistry, 295, pp. 177-195.

Chiappe, C., Malvaldi, M., Pomelli, C.S.The solvent effect on the Diels-Alder reaction in ionic liquids: Multiparameter linear solvation energy relationships and theoretical analysis(2010) Green Chemistry, 12 (8), pp. 1330-1339.

Malvaldi, M., Chiappe, C.Excess entropy scaling of diffusion in room-temperature ionic liquids(2010) Journal of Chemical Physics, 132 (24), art. no. 244502, .

Vecchi, A., Chambery, A., Chiappe, C., Marra, A., Dondoni, A.Copper(I)-catalyzed azide-alkyne cycloadditions in ionic liquids under amine-free conditions(2010) Synthesis, (12), art. no. T02710SS, pp. 2043-2048.

Angelini, G., De Maria, P., Chiappe, C., Fontana, A., Pierini, M., Siani, G.Basicity of pyridine and some substituted pyridines in ionic liquids(2010) Journal of Organic Chemistry, 75 (11), pp. 3912-3915.

Fukuhara, G., Chiappe, C., Mele, A., Melai, B., Bellina, F., Inoue, Y.Photochirogenesis in chiral ionic liquid: Enantiodifferentiating [4+4] photocyclodimerization of 2-anthracenecarboxylic acid in (R)-1-methyl-3-(2,3- dihydroxypropyl)imidazolium bistriflimide(2010) Chemical Communications, 46 (20), pp. 3472-3474.

Chiappe, C., Signori, F., Valentini, G., Marchetti, L., Pomelli, C.S., Bellina, F.Novel (Glycerol)borate-based ionic liquids: An experimental and theoretical study(2010) Journal of Physical Chemistry B, 114 (15), pp. 5082-5088.

Bellina, F., Chiappe, C.The heck reaction in ionic liquids: Progress and challenges(2010) Molecules, 15 (4), pp. 2211-2245.

Chiappe, C., Mennucci, B., Silvio Pomelli, C., Sanzone, A., Marra, A.A theoretical study of the copper(i)-catalyzed 1,3-dipolar cycloaddition reaction in dabco-based ionic liquids: The anion effect on regioselectivity(2010) Physical Chemistry Chemical Physics, 12 (8), pp. 1958-1962.

Cui, Y., Biondi, I., Chaubey, M., Yang, X., Fei, Z., Scopelliti, R., Hartinger, C.G., Li, Y., Chiappe, C., Dyson, P.J.Nitrile-functionalized pyrrolidinium ionic liquids as solvents for cross-coupling reactions involving in situ generated nanoparticle catalyst reservoirs(2010) Physical Chemistry Chemical Physics, 12 (8), pp. 1834-1841.

Chiappe, C., Malvaldi, M., Melai, B., Fantini, S., Bardi, U., Caporali, S.An unusual common ion effect promotes dissolution of metal salts in room-temperature ionic liquids: A strategy to obtain ionic liquids having organic-inorganic mixed cations(2010) Green Chemistry, 12 (1), pp. 77-80.

Chiappe, C., Malvaldi, M., Pomelli, C.S.Ab initio study of the Diels-Alder reaction of cyclopentadiene with acrolein in a ionic liquid by KS-DFT/3D-RISM-KH theory(2010) Journal of Chemical Theory and Computation, 6 (1), pp. 179-183.

Bini, R., Chiappe, C., Marchetti, F., Pampaloni, G., Zacchini, S.Structures and unusual rearrangements of coordination adducts of MX 5 (M = Nb, Ta; X = F, Cl) with simple diethers. a crystallographic, spectroscopic, and computational study(2010) Inorganic Chemistry, 49 (1), pp. 339-351.

Lanza, T., Minozzi, M., Monesi, A., Nanni, D., Spagnolo, P., Chiappe, C.Radical additions of thiols to alkenes and alkynes in ionic liquids(2009) Current Organic Chemistry, 13 (17), pp. 1726-1732. ‘+Chiappe, C., Melai, B., Sanzone, A., Valentini, G.Basic ionic liquids based on monoquaternized 1,4-diazobicyclo[2.2.2]octane (dabco) and dicyanamide anion: Physicochemical and solvent properties (2009) Pure and Applied Chemistry, 81 (11), pp. 2035-2043. +’

Bini, R., Chiappe, C., Pomelli, C.S., Parisi, B.Effect of ionic liquids on the Menschutkin reaction: An experimental and theoretical study(2009) Journal of Organic Chemistry, 74 (22), pp. 8522-8530.

Angelini, G., De Maria, P., Chiappe, C., Fontana, A., Gasbarri, C., Siani, G.The base-catalyzed keto-enol interconversion of 2-nitrocyclohexanone in ionic liquids(2009) Journal of Organic Chemistry, 74 (17), pp. 6572-6576.

Bini, R., Chiappe, C., Mestre, V.L., Pomelli, C.S., Welton, T.A theoretical study of the solvent effect on Diels-Alder reaction in room temperature ionic liquids using a supermolecular approach(2009) Theoretical Chemistry Accounts, 123 (3-4), pp. 347-352.

Bellina, F., Bertoli, A., Melai, B., Scalesse, F., Signori, F., Chiappe, C.Synthesis and properties of glycerylimidazolium based ionic liquids: A promising class of task-specific ionic liquids(2009) Green Chemistry, 11 (5), pp. 622-629.

Chiappe, C., Malvaldi, M., Pomelli, C.S.Ionic liquids: Solvation ability and polarity(2009) Pure and Applied Chemistry, 81 (4), pp. 767-776.

Pretti, C., Chiappe, C., Baldetti, I., Brunini, S., Monni, G., Intorre, L.Acute toxicity of ionic liquids for three freshwater organisms: Pseudokirchneriella subcapitata, Daphnia magna and Danio rerio(2009) Ecotoxicology and Environmental Safety, 72 (4), pp. 1170-1176.

Malvaldi, M., Bruzzone, S., Chiappe, C., Gusarov, S., Kovalenko, A.Ab initio study of ionic liquids by KS-DFT/3D-RISM-KH theory(2009) Journal of Physical Chemistry B, 113 (11), pp. 3536-3542.

Baciocchi, E., Chiappe, C., Del Giacco, T., Fasciani, C., Lanzalunga, O., Lapi, A., Melai, B.Reaction of singlet oxygen with thioanisole in ionic liquids: A solvent induced mechanistic dichotomy(2009) Organic Letters, 11 (6), pp. 1413-1416.