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The synthesis of a novel polyhedral oligomeric silsesquioxane functionalized with eight rigid and directional terpyridine-based arms (Ter-POSS) was successfully achieved via a Sonogashira reaction. The POSS based ligand was extensively characterized using different techniques including 1H, 13C and 29Si NMR as well as UV-Vis and fluorescence spectroscopies. The assembly of these nano-caged units in the presence of different transition metal ions (Fe2+, Zn2+ and Cu2+) as well as of a cation from the lanthanides (Eu3+) was investigated using absorption and emission spectroscopies. The final materials display an evident emission in different regions of the visible spectrum as a function of the cation employed. Additional insights into the structural organization of Ter-POSS in the presence of metal cations were obtained via molecular mechanics and molecular dynamics simulations. The polymeric material resulting from the complexation with europium displays a white light emission ascribed to the presence of combined contributions from the blue, green and red regions. The final self-assembled organizations display an increased quantum yield with the highest value (29.6%) obtained in the presence of Zn2+. Moreover, the white-light emitting europium-based nanostructure exhibits one of the highest quantum yields reported in the literature for similar solids.

Carbon nanotubes have been covalently functionalized with catechol moieties through the formation of the corresponding aryl radicals obtained by reacting 4-aminocatechol with isoamyl nitrite. The functionalized multiwalled carbon nanotubes have been in turn used to immobilize Pd(II) ions on its surface forming catechol-Pd complexes, which were reduced to Pd nanoparticles (NPs). The so-obtained hybrid material has been characterized by means of thermogravimetric analysis coupled with differential scanning calorimetry (TGA-DSC), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). This latter technique allowed to estimate the nanoparticle size (5.7 +/- 2.8 nm) whereas a palladium loading of 20.3 wt % has been found by inductively coupled plasma optical emission spectroscopy (ICP-OES). The carbon nanotube-catechol-Pd hybrid was used as catalyst in two C-C coupling reactions, namely Suzuki and Heck reactions, resulting recyclable for at least 9 times in the latter process. During the reuse Pd nanoparticles increase their dimension to 19.3 +/- 11.7 nm.

Polyhedral oligomeric silsesquioxanes (POSS) are organic-inorganic hybrid molecules piquing the interest of researchers thanks to their synergistic features. The great versatility of POSS nanostructures arises from the easy tunability of peripheral organic moieties combined with the high thermal and chemical stability of the inner inorganic core. In this review, we highlight the use of POSS nanostructures as molecular precursors for the synthesis of homogeneous and heterogeneous catalysts able to promote many processes including alkene epoxidation, C-C bond formation, CO2 conversion, "click reactions", hydrogenation, and ethylene polymerisation, among others. In this scenario, POSS units found application as molecular models for single-site heterogeneous catalysts, stabilising platforms for metal nanoparticles, metal ligands, supports for organic salts, and molecular building blocks for the design of ionic polymers. Herein, we address the catalytic application of POSS nanostructures with the purpose of encouraging the development of performing hybrid catalysts with tailored properties.

The increased awareness of the catastrophic consequences caused by the accumulation of greenhouse gases into the atmosphere has generated a large mobilization aimed at CO2 mitigation. Herein, in the spirit of the transformation of a waste as CO2 into value added products, we propose an efficient preparation of two different hybrid systems based on aluminum chloride tetrastyrylporphyrin (TSP-Al-Cl) and 1,4-butanediyl-3,3′-bis-1-vinylimidazolium dibromide copolymerized in the presence (MWCNT-TSP-AlCl-imi) and in absence (TSP-AlCl-imi) of multi-walled carbon nanotubes (MWCNTs) for the CO2 utilization in the synthesis of cyclic carbonates. The so-prepared materials have been thoroughly characterized by means of several spectroscopic and analytical techniques. The MWCNT-TSP-AlCl-imi heterogenous catalyst enabled the highly efficient chemical transformation of CO2 and epoxides into cyclic carbonates with high turnover number (TON) and frequency (TOF) values at low temperature down to 30 °C in solvent-free conditions. MWCNT-TSP-AlCl-imi proved to be a very stable and reusable heterogeneous catalyst in consecutive cycles without the need of any reactivation procedure and no leaching phenomena. Furthermore, the optimal morphology of MWCNT-TSP-AlCl-imi, with the crosslinked polymer uniformly distributed onto MWCNTs backbone, resulted in a more active catalyst with a TON double than the unsupported one. The enhanced activity of MWCNT-TSP-AlCl-imi can be ascribed to its higher surface area that permits fully accessible catalytic sites. Interestingly, MWCNT-TSP-AlCl-imi also showed a catalytic activity comparable to a reference homogeneous catalytic system, proving that synergism occurred between the metal centers and the nucleophilic sites due to their close proximity.

The hydrolysis of 3-ammoniumpropylbis(catecholato)silicate 1, giving two different silica-based materials containing different amounts of tris(catecholato)silicate, is reported. The latter species can be formed through an attack of catechol to the silicon atom in the pentacoordinate complex, in which the silicon-carbon bond is further activated toward electrophilic proton cleavage. The Knoevenagel reaction was used as a probe in order to test the availability of functional groups on the surface of such materials.

The aim of this Perspective is to start a discussion about the real usefulness of more or less sophisticated catalytic systems for the Knoevenagel reaction with malononitrile, a reaction that can take place under mild conditions without the need of a catalyst. From a sustainable viewpoint the questions are: Is it useful to increase the rate of a reaction that already occurs under mild conditions? Is it useful to spend resources and time in designing, characterizing and realizing complex catalytic systems for such reaction? Does it make sense to carry out the reaction under conditions such as to have a slower reaction rate and therefore to find a catalyst that is able to increase it?

We report the first example of successful heterogenization of the classical PdI42- carbonylation catalyst, achieved in two simple steps from ionic liquid-functionalized multi-walled carbon nanotubes (MWCNTs). The newly developed materials (PdI4@MWCNT-imi-X, X = Br, I) present the PdI42- anion supported on an imidazolium network (imi) grown on MWCNTs and have been fully characterized. The activity of PdI4@MWCNT-imi-X has been successfully tested in a paradigmatic carbonylation reaction, the oxidative monoaminocarbonylation of 1-alkynes with amines to give high value added 2-ynamides (obtained in good yields, 50–84%, starting from various substrates). The heterogeneous catalyst could be easily recycled and showed a good efficiency even after the fourth recycle, when deactivation began to occur owing to the formation of inactive Pd(0) species, as confirmed by XPS analysis. Hot and cold filtration tests were compatible with an essentially heterogeneous catalytic process, and limited metal contamination in the final organic compounds occurred, as assessed by ICP-MS analysis of representative carbonylation products.

Two heterogeneous catalysts were prepared with the aim of following the promising path of CO2 fixation into epoxides. The synthetic procedure involves a radical copolymerization of an octavinylsilsesquioxane as inorganic core building block and tetrastyrylporphyrin aluminum chloride monomer (TSP-AlCl) in presence (POSS-TSP-AlCl-imiBr) or in absence (POSS-TSP-AlCl) of a bis-vinylimidazolium bromide salt (bis-imiBr), in order to investigate if the bifunctional heterogeneous material can display better catalytic performance than the separate species. All the solids were fully characterized and tested in the synthesis of cyclic carbonates starting from CO2 and several epoxides. The synergic cooperation of the two co-catalytic species (Lewis acid/imiBr) was observed. POSS-TSP-AlCl-imiBr showed to be a recyclable material with an excellent activity and TON and TOF values up to 16,000 and 5000, respectively. These excellent results, even under mild reaction and solvent-free conditions, were attributed to a twofold effect: the proximity between the two active sites due to the direct covalent bond between the porphyrin and the imidazolium component and the increasing local concentration of active sites effect that is obtained by functionalizing the silica cage at all its vertices.

Taking inspiration from the chemistry of dopamine, a simple and economic synthetic approach toward the synthesis of a series of silica-based polydopamine-like materials has been developed. Mild conditions and easy manipulation are the strongest aspects of this methodology. Such hybrid materials were successfully used as recyclable catalysts for Knoevenagel reactions., A simple one-pot procedure under mild conditions has been developed with the aim of preparing a set of hybrid organic-inorganic multifunctional materials. This procedure is based on the use of catechol and KIO 4 as oxidizing agent in conjunction with 3-aminopropyl-, substituted 3-aminopropyl- and 3-methylimidazolium-1-trimethoxypropylsilane mimicking polydopamine-like chemistry. Reactions were carried out in water at room temperature and 70 °C to give fifteen materials that were characterised by using several techniques (nitrogen physisorption, TGA, XPS, 13C and 29Si CP-MAS NMR, IR, pH PZC). Knoevenagel reaction was chosen as a good probe to investigate the availability of functional groups on the surface of the materials. The most active catalytic materials were tested in recycling procedures. Such simple procedure is of broad interest for the scientific community and it open the doors to the development of new hybrid organic-inorganic multifunctional materials for several purposes.

Three different carbon nanoforms (CNFs), single-walled and multi-walled carbon nanotubes (SWCNTs, MWCNTs) and carbon nanohorns (CNHs), have been used as supports for the direct polymerization of variable amounts of a bis-vinylimidazolium salt. Transmission electron microscopy confirmed that all CNFs act as templates on the growth of the polymeric network, which perfectly covers the nanocarbons forming a cylindrical (SWCNTs, MWCNTs) or spherical (CNHs) coating. The stability of these hybrid materials was investigated in the conversion of CO2 into cyclic carbonate under high temperature and CO2 pressure. Compared with the homopolymerized monomer, nanotube-based materials display an improved catalytic activity. Beside the low catalytic loading (0.05–0.09 mol%) and the absence of Lewis acid co-catalysts, all the materials showed high TON values (up to 1154 for epichlorohydrin with SW-1:2). Interestingly, despite the loss of part of the polymeric coating for crumbling or peeling, the activity increases upon recycling of the materials, and this behaviour was ascribed to their change in morphology, which led to materials with higher surface areas and with more accessible catalytic sites. Transmission electron microscopy analysis, along with different experiments, have been carried out in order to elucidate these findings.

Supported imidazolium modified polyhedral oligomeric silsesquioxanes (POSS) on SBA-15 have been used as platform for Pd(II) species. The so-obtained material was firstly characterized by means of TGA, solid state NMR, TEM, XPS, SAXS, porosimetry and ICP-OES and it was successfully tested as pre-catalyst in C−C cross couplings, namely Suzuki-Miyaura and Heck reactions. In both cases, the solid proved to be highly efficient and easily recoverable from the reaction mixture. The recyclability was verified for up to seven cycles without showing any activity decrease. Interestingly, only Pd(II) was detected in the reused catalyst in the Heck reaction. Therefore, the versatility of the material was investigated by using various aryl halides. Our palladium nanocomposite was able to promote both Suzuki and Heck reactions down to 0.0007 mol% showing outstanding turnover frequency (TOF) values of 114,286 and 32,381 h −1 , respectively. Comparison with the palladium catalyst on SiO 2 -POSS-imidazolium support showed interesting differences in terms of stabilization of Pd species and recyclability. The excellent outcome of the reactions could be ascribed to the textural properties of the SBA-15 support and the presence of the imidazolium-POSS nanocage within the pores of SBA-15, that worked as a sort of nanoreactor. (Figure presented.).

A straightforward and economic procedure has been developed for the synthesis of a new polydopamine-like silica-based material that has been obtained by oxidation of catechol with KIO4 followed by reaction with 3-aminopropyltrimethoxysilane. All techniques adopted for characterization showed that the obtained material is rich in different functional groups and the morphological analyses revealed dimensions in the nanometric range. The hybrid material has been characterized by several techniques showing its polydopamine-like nature, and preliminary observations for dye adsorption have been reported., University of Palermo PRIN2017- 2017YJMPZN

A facile method to produce paper&ndash, TiO2 decorated with AgBr nanoparticles by a mild hydrothermal process at 140 &deg, C was reported. The synthesis method was based on the immersion of the paper in a ready-made suspension of TiO2/AgBr, comprising TiO2 sol solution prepared in acidic conditions and AgBr solution (10&minus, 4 M). A paper&ndash, TiO2 sample was prepared and used as reference. The formation of crystalline phases of titanium oxide (TiO2) and silver bromide (AgBr) was demonstrated by XRD, Raman and EDX analyses. The surface morphology of the TiO2&ndash, AgBr was investigated by Field Effect Scanning Electronic Microscopy (FE&ndash, SEM). The photocatalytic performances of the prepared material were evaluated in the degradation of 2-propanol in the gas phase, under simulated sunlight illumination. Its antibacterial properties against Escherichia coli (E. coli) were also assessed. The efficiency of photodegradation and the anti-bacterial properties of paper&ndash, TiO2&ndash, AgBr were attributed to an improvement in the absorption of visible light, the increased production of reactive oxygen species (ROS) and the low recombination of photogenerated charge carriers due to the synergistic effect between TiO2 and AgBr/Ag nanoparticles.

[EN] Hybrid nanostructures with switchable and reversible "blue-red-green" emission were efficiently synthesized. These nanostructures comprise polyhedral oligomeric silsesquioxanes (POSS) that behave as a nanocage that can be functionalized with terpyridine-based organic ligands, which can be easily complexed with europium (III) ions. The complexes were characterized by UV-Vis and fluorescence spectroscopy and their stoichiometry was also confirmed by H-1 NMR spectroscopy. In the presence of the Eu(III) ions, the octafunctionalized nanocages self-assemble to form 3D architectures that display an intense red-emission, especially in the solid state. The presence of an alkenyl group bridging the inorganic core to the organic moiety was employed to tune the emission properties by trans-cis isomerization of the double bond. In the case of the octafunctionalized nanocages (O-POSS), this isomerization was monitored in the presence of Eu(III) cations and was accompanied by an evident colour change from blue (trans-O-POSS) to red (Eu@trans-O-POSS) and finally to green (cis-O-POSS) as consequence of the release of the metal cations. This behaviour, together with the easy dispersion of the dry powder and the possibility of coating as a film in presence of small amounts of solvent, makes the emissive solid promising for applications in materials science., The authors acknowledge the University of Palermo and the University of Namur. V.C. gratefully acknowledges the University of Palermo and University of Namur for a co-funded PhD fellowship.

Multiwalled carbon nanotubes (MWCNTs) were easily and efficiently functionalised with highly cross-linked polyamines. The radical polymerisation of two bis-vinylimidazolium salts in the presence of pristine MWCNTs and azobisisobutyronitrile (AIBN) as a radical initiator led to the formation of materials with a high functionalisation degree. The subsequent treatment with sodium borohydride gave rise to the reduction of imidazolium moieties with the concomitant formation of secondary and tertiary amino groups. The obtained materials were characterised by thermogravimetric analysis (TGA), elemental analysis, solid state 13C-NMR, Fourier-transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), potentiometric titration, and temperature programmed desorption of carbon dioxide (CO2-TPD). One of the prepared materials was tested as a heterogeneous base catalyst in C-C bond forming reactions such as the Knoevenagel condensation and Henry reaction. Furthermore, two examples concerning a sequential one-pot approach involving two consecutive reactions, namely Knoevenagel and Michael reactions, were reported. This journal is

Two simple routes for the synthesis of a paper-TiO2 composite were tuned up and the efficiency of the resulting paper-TiO2 photocatalyst was investigated in the 2-propanol oxidation in gas phase. The first route involved the in-situ generation over the sheet of paper of a TiO2 layer starting from a solution of Ti (OBu)4 in tert-butanoliacetic acid, followed by hydrothermal treatment at 120 degrees C for 3 h. The sample was labelled as paper-TiO2 (H). The second approach was based on the adsorption on the paper of a ready-made suspension of titania nanoparticles (TiO2 sol), generated in autoclave at 140 degrees C and stable in acid medium at pH

A new class of copolymers containing oligothiophene moieties with different lengths and fullerene units have been designed and prepared by an easy and inexpensive one-step synthetic approach. The incorporation of small quantities of these copolymers into bulk heterojunction (BHJ) solar cells with donor regioregular polythiophene (P3HT) and an acceptor fullerene derivate (PCBM) results in good control of the phase separation process without further affecting the BHJ optoelectronic properties. Indeed, under thermal annealing these copolymers allow the modulation of the growth of domains whose size depends on the length of the copolymer repetitive units. Domain size on the same length scale as the P3HT exciton diffusion length with a good continuity between the electrodes gives efficient exciton dissociation and charge mobility. Thus by employing copolymers containing oligothiophenic chains with a size of about 8 nm, the power conversion efficiency (PCE) (4.46%) and short current density (JSC) (16.15 mA cm−2) values are the highest reported so far for P3HT:PCBM solar cells on plastic substrates.

Six new hybrid materials composed of carbon nanohorns (CNHs) and highly cross-linked imidazolium salts were easily synthesized using a one-step procedure based on the radical oligomerization of bis-vinylimidazolium salts (bVImiX) in the presence of pristine CNHs. The hybrid materials were characterized and employed as the sole catalysts for the conversion of carbon dioxide into cyclic carbonate by reaction with epoxides. The solids displayed excellent turnover number and productivity. Moreover, four catalysts were investigated in recycling experiments. Two catalysts containing an octyl linker between the imidazolium units and a bromide or an iodide anion showed no loss in activity after three cycles. The other two catalysts containing a p-xylyl linker and a bromide anion and different CNHs/bVImiX ratios showed an unprecedented increase of activity after recycling.

Two different carbon nanoforms (CNFs), namely multi-walled carbon nanotubes (MWCNTs) and carbon nanohorns (CNHs), have been chosen as support for the direct polymerization of a bis-vinylimidazolium salt. Transmission electron microscopy analyses revealed a templating effect of the CNFs on the growth of the polymeric network, which perfectly covers their whole surfaces creating a cylindrical or spherical coating for MWCNTs and CNHs, respectively. Subsequently, the CNFs-polyimidazolium have been used as stabilizers for Pd nanoparticles (Pd NPs), and the obtained materials have been characterized by means of analytical and spectroscopic techniques and then employed as easily recoverable and recyclable catalysts for Suzuki and Heck reactions. Quantitative conversions have been obtained in almost all the explored reactions, even employing low loading of catalyst (down to 0.007 mol%). Suzuki reactions were carried out in pure water under aerobic conditions. Both materials showed excellent activity and recyclability for the investigated C-C coupling reactions, with the CNHs-based material resulting slightly more active than the MWCNTs-based one due to a higher superficial exposure of Pd NPs.

Hypothesis Polydopamine (PDA) is widely used as hydrophilic coating for several applications. However, most of the methods studied to improve or manipulate PDA properties are multistep and time-consuming, and there is a need for versatile strategies aimed at controlling and modifying the properties of PDA. Experiments PDA-halloysite nanocomposites were produced under different oxidation conditions in alkaline and acidic media and were characterized by UV–visible and attenuated total refraction- Fourier Transform Infrared spectroscopies, thermogravimetric analysis, porosimetry, scanning electron microscopy, X-ray diffraction and contact angle measurements against the reference PDA polymer. Findings Inclusion of the inorganic halloysite nanofiller in the PDA component was found to affect the thermal properties of the nanocomposite as well as its structure, depending on the experimental conditions. The ability of the nanocomposites to adsorb organic dyes as possible membrane coatings for environmental remediation was also investigated by different models, suggesting promising applications as adsorbents for the treatment of wastewaters.

Polyhedral oligomeric silsesquioxanes (POSS) have been employed as molecular building blocks for the synthesis of imidazolium cross-linked networks, to be used as heterogeneous catalysts for the conversion of carbon dioxide into cyclic carbonates. Two hybrid materials with different nucleophilic species (bromide and iodide) have been prepared and characterized by means of elemental analysis, 13C and 29Si solid-state NMR spectroscopy, thermogravimetric analysis and IR spectroscopy. The solids were tested as the sole catalyst under metal- and solvent-free reaction conditions showing full selectivity toward the formation of cyclic carbonates. High turnover number (TON) and productivity values, up to 5502 and 1081 respectively for glycidol conversion at 100 °C and up to 4942 and 1122 for epichlorohydrin conversion at 150 °C after 3 h, were obtained. Such outstanding productivity values were ascribed to the optimal organic/inorganic (i. e., imidazolium moiety/POSS support) weight ratio. The recyclability of the materials was successfully verified for five consecutive runs allowing their consideration as promising candidates for continuous flow technologies.

The application of nanocarbons as useful scaffolds for the production of a wide range of catalytic systems is an ever-growing field as witnessed by the huge amount of research on this topic. Both covalent and non-covalent modifications of nanocarbons represent the main routes to gain access to hybrid nanostructured catalysts. In this chapter the attention will be focused on nanocarbons, namely, fullerene, nanotubes, and graphene, employed for catalytic purposes covering both organocatalytic and metal-based (metal nanoparticles, organometallic complexes) reactions, whereas simple physical mixtures of nanocarbons and metal nanoparticles as well as examples dealing with electrocatalysis or photocatalysis are out of the scope of the present chapter. Because of the large number of publications in this field, we dealt some recent examples that represent a short overview on this topic that are not meant to be exhaustive but merely representatives of the subject.

In this contribution, we present a chemically efficient and sustainable protocol for the palladium-catalyzed copper-free Sonogashira cross-coupling reaction, based on the use of a heterogeneous catalytic system. This consists in the combination of a palladium catalyst on highly cross-linked thiazolidine network on silica and a polystyrene-supported base. The solid catalyst/base system acts as a palladium scavenger avoiding leaching of the metal and consequent product contamination. The reaction can be conducted in safe and easily recoverable acetonitrile/water azeotrope as reaction medium. This proved to be an efficient greener alternative to the classic toxic aprotic media commonly used in cross-coupling reaction, such as DMF and NMP. Acetonitrile/water azeotrope could be easily recovered and reused allowing the minimization of waste production. Our approach, based on the use of both a supported base and a supported catalyst, has proven to be efficient for the waste reduction, as proved by the low E-factor values achieved.

We report the synthesis and catalytic properties of single-walled carbon nanotube-polyamidoamine dendrimers hybrids (SWCNT-PAMAM), prepared via a convergent strategy. The direct reaction of cystamine-based PAMAM dendrimers (generations 2.5 and 3.0) with pristine SWCNTs in refluxing toluene, followed by immobilization and reduction of [PdCl4](2-), led to the formation of highly dispersed small palladium nanoparticles homogeneously confined throughout the nanotube length. One of these functional materials proved to be an efficient catalyst in Suzuki and Heck reactions, able to promote the above processes down to 0.002 mol % showing a turnover number (TON) of 48 000 and a turnover frequency (TOF) of 566 000 h(-1). In addition, the hybrid material could be recovered and recycled for up to 6 times. No leaching of the metal has been detected during the Suzuki coupling. Additional experiments carried out on the spent catalyst permitted to suggest that a "release and catch" mechanism is operative in both reactions, although during Heck reaction small catalytically active soluble Pd species are also present.

Single walled carbon nanotubes (SWCNTs) were functionalized with imidazolium salts bearing vinyl functionalities. An extremely high loading of active species was achieved through a straightforward one-pot procedure involving self-assembly of the imidazolium moieties followed by radical initiated polymerization of the double bonds. The materials were extensively characterized by transmission electron microscopy, Raman spectroscopy, nitrogen physisorption and combustion chemical analysis. The imidazolium functionalized SWCNTs displayed excellent catalytic activity for the reaction of CO2 and epoxides to produce cyclic carbonates as demonstrated by the excellent turnover numbers (TON). Moreover, they were used in multiple catalytic cycles without loss of activity.

Hybrid paper-TiO2, paper-Cu2O-TiO2 and paper-TiO2-Cu2O photocatalysts were prepared via a non-hydrolytic sol-gel process followed by mild hydrothermal treatment to generate the TiO2 layer, and a reduction process to form the Cu2O nanoparticles. The hybrid photocatalysts have been characterized by Raman, TGA, FE-SEM, UV-Vis and XPS. The immobilized TiO2 was found to form a homogeneous thin layer composed of nanoparticles with a size smaller than 10 nm. The Cu2O nanoparticles with sizes of 30-100 nm were generated either on the top of the TiO2 layer or by reduction of Cu2+ ions. All the prepared hybrid catalysts showed efficient photocatalytic properties for the degradation of toluidine when exposed to simulant solar light. A strong enhancement in the photocatalytic activity was observed when TiO2 was coupled with the Cu2O heterojunction, with the highest effect being observed when the Cu2O NPs were present on top of the TiO2 layer. The hybrid photocatalyst can be reused for at least four consecutive cycles without a significant decrease in the degradation efficiency. The preparation technique of the hybrid catalyst is reliable, economic, easy to implement and may be scaled to prepare paper-TiO2 hybrid photocatalysts active under sun-light exposure.

Supported ionic liquids (SILs) represent a class of materials with peculiar properties and a huge potential regarding their possible applications in different fields of chemistry. Herein, we report our ongoing research about the use of SILs as support for organocatalysts, their role as catalysts themselves, and their application as support and stabilizers of palladium nanoparticles (PdNPs). The use of SILs based materials allowed achieving good results. Moreover, in some cases, after the functionalization of the catalytic species with an ion-tag moiety, a release and catch approach was employed in order to improve the catalytic activity and to facilitate the recovery of the hybrid system formed by the catalyst adsorbed onto SILs materials. All the reported examples demonstrate the versatility of such SILs materials, which can represent powerful tools able to exert a large number of functions.

A highly sustainable and waste-minimized protocol for Heck coupling has been defined. Optimal conditions have been defined by exploiting a heterogeneous catalyst based on supported ionic liquid-like phases featuring high Pd loading (10 wt %) and by optimizing its efficiency in a recoverable green reaction medium (acetonitrile/water azeotrope). Pure products 4a–l and 6a–h have been isolated chromatography-free in high yields (74–99%) and with extremely low environmental factor (E-factor) values (2.3–5.0). With the application of flow technology, the selected heterogeneous base and Pd catalyst have been fully recovered and reused, and minimum palladium leaching allowed for isolation of the final products with low residual palladium content (

Two polystyrene-supported and six homogeneous MacMillan imidazolidinone catalysts were prepared and tested for the asymmetric α-alkylation of propanal with benzodithiolylium tetrafluoroborate. The chiral imidazolidinone was linked to polystyrene through the N-3 atom or through the phenyl ring and their catalytic activity was compared with that of their unsupported precursors. This comparison has allowed us to find an unsupported catalyst that displays high catalytic activity down to 5 or 2 mol % at room temperature with a high level of enantioselectivity also when used with hexanal and 3-phenylpropanal. In addition, one of the heterogeneous materials was revealed to be highly recyclable for at least eight cycles with no loss in efficiency working at the same levels of activity and enantioselectivity as the unsupported counterpart.

Highly cross-linked imidazolium-based materials, obtained by radical oligomerization of bis-vinylimidazolium salts in the presence of 3-mercaptopropyl-modified silica gel, were used as supports for palladium catalysts. Thanks to the high imidazolium loading these materials were able to support a high amount of the metal (10 wt%). Such materials were characterized by several techniques (13C magic angle spinning nuclear magnetic resonance, the Brunauer-Emmett-Teller technique, X-ray photoelectron spectroscopy, and transmission electron microscopy). The palladium catalysts displayed good activity allowing the synthesis of several biphenyl compounds in high yields working with only 0.1 mol% of palladium loading at 50°C in ethanol/water under batch condition. Moreover, a flow apparatus, to optimize the efficiency of the isolation of the pure products and minimize waste (E-factor), was investigated. For the first time the palladium catalyst and base (K 2CO3) were placed in two separate columns allowing an easy recovery of the products with very low E-factor values (

In this review, the most recent advances (2014–2016) on the synthesis of new polymer-supported catalysts are reported, focusing the attention on the synthetic strategies developed for their preparation. The polymer-supported catalysts examined will be organic-based polymers and organic-inorganic hybrids and will include, among others, polystyrenes, poly-ionic liquids, chiral ionic polymers, dendrimers, carbon nanotubes, as well as silica and halloysite-based catalysts. Selected examples will show the synthesis and application in the field of organocatalysis and metal-based catalysis both for non-asymmetric and asymmetric transformations.

In this review, the most recent advances in the synthesis and catalytic applications of covalently supported ionic liquid (IL) phases will be discussed. This class of recyclable catalytic materials is based on the covalent attachment of several types of ammonium salts, usually imidazolium, but also thiazolium, triazolium, and pyrrolidinium salts, on the surface of different supports, for example, silica, periodic mesoporous organosilica, polystyrene, magnetic-based materials, carbon nanotubes (NTs), halloysite NTs, polyhedral oligomeric silsesquioxane (POSS), and fullerenes. Moreover, poly(ionic liquid) materials, in which the IL-based structure also acts as a support, will be considered. The synthetic applications of these materials will be presented, with special emphasis on their roles as catalysts, without added organocatalysts or metal-based catalysts, as supports for organocatalysts, and as supports for metal-based catalysts.

The surfaces of multi-walled carbon nanotubes (MWCNTs) were non-covalently modified using two bis-imidazolium dibromide derivatives having phenyl or pyrene groups. Due to the presence of the two pyrene groups the bis(pyren-1-ylmethylimidazolium) dibromide derivative was immobilised at a loading of about 15-16 wt %, whereas only

A C60-ionic liquid hybrid has been covalently linked to three different solid supports, namely amorphous silica, SBA-15 and Fe2O3@SiO2, and the resulting materials have been employed as covalently supported ionic liquid phases (cSILP) in order to immobilize and stabilize palladium nanoparticles (PdNPs). These novel hybrid materials are based on a sort of "matryoshka" system (PdNPs@imidazolium-salt@C60@support) in which the imidazolium-based moieties have not been directly linked to the surface of the support, but they are present in an octopus-like spatial arrangement on the uniformly surface-distributed fullerenes. These materials have been fully characterized and successfully employed as catalysts in C-C bond forming reactions showing, in the case of Suzuki cross-coupling, an outstanding catalytic activity both under classical heating and by irradiating with microwaves. Turn-over frequencies (TOFs) of up to 3640000 h-1 have been achieved and the silica-based catalyst showed full recyclability even after 10 cycles.

DNA-binding investigations showed that two different derivatives endowed with pyrene and imidazolium moieties, 1 and 2, strongly bind both double-stranded DNA and telomeric sequences in G-quadruplex (G4) conformation. The values of the DNA-binding constants indicate that 1 and 2 show preferential affinity for G4-DNA, of about one and two orders of magnitude, respectively. Moreover, 1 and 2 inhibit short and long-term proliferation of breast cancer cell lines in a time- and dose-dependent fashion. Remarkably, senescence assays indicate that telomeric G4-DNA is a possible biotarget for the cytotoxic activity of 2. Molecular dynamics simulations suggest that the stronger binding of 2 with G4-DNA and the related senescence induction, are a consequence of additional edge-to-face interactions with a base in the TTA loop.

A polyhedral oligomeric silsesquioxane-imidazolium tetrachloropalladate salt (POSS-Imi-PdCl4) was prepared by the reaction of a polyhedral oligomeric silsesquioxane-imidazolium chloride salt (POSS-Imi-Cl) with PdCl2 and used as a pre-catalyst for the Suzuki-Miyaura reaction in water at 100 °C at a low loading (0.08-0.16 mol %). Biphenyl compounds were isolated in high to excellent yields. A comparison of the POSS-based catalyst with the corresponding catalyst without the nanocage structure (i.e., 1-butyl-3-methylimidazolium tetrachloropalladate) highlighted the role of the POSS structure to reach higher yields in the Suzuki-Miyaura reaction. This result is ascribed to a proximity effect of the imidazolium moieties linked to the nanocage structure. Fresh and used catalytic materials were characterised by using X-ray photoelectron spectroscopy and TEM.

An innovative two stage liquid–liquid biphasic homogeneous protocol for the asymmetric organocatalytic aldol reaction is proposed, based on the use of the cis-ion-tagged proline 8 dissolved in the liquid film of a multilayered ionic liquid covalently bonded to silica gel 4. The resulting catalytically active material 9 is first soaked with cyclohexanone in the presence of water, resulting in a semi-transparent gel, then the aldehyde is added and the mixture stirred at RT. In the first stage, 4 acts as a catalyst reservoir that delivers 8 to the cyclohexanone phase allowing the reaction to take place homogeneously. In the second stage, cyclohexanone is removed under vacuum and the resulting slurry is extracted with anhydrous diethylether. Now 4 acts as a catalyst sponge, redissolving 8. Product extraction is extremely selective; no trace of catalyst is detected in the product-containing phase, and 9 can be easily reused several times with high cumulative productivity values (up to 523).

Asymmetric organocatalysis is now recognized as the third pillar of asymmetric synthesis. Recent years have witnessed increasing interest towards the use of highly active and stereoselective organocatalysts. This critical review documents the advances in the development of chiral organocatalysts which are systematically used in ≤3 mol% loading in all the sub-areas of the field, namely aminocatalysis, Brønsted acids and bases, Lewis acids and bases, hydrogen bond-mediated catalysis, phase transfer and N-heterocyclic carbene catalyses (194 references).

Multilayered, covalently supported ionic liquid phase (mlc-SILP) materials were synthesized by using a new approach based on the grafting of bis-vinylimidazolium salts on different types of silica or polymeric supports. The obtained materials were characterized and tested as catalysts in the reaction of supercritical carbon dioxide with various epoxides to produce cyclic carbonates. The material prepared by supporting a bromide bis-imidazolium salt on the ordered mesoporous silica SBA-15 was identified as the most active catalyst for the synthesis of cyclic carbonates and displayed improved productivity compared with known supported ionic liquid catalysts. The catalyst retained its high activity upon reuse in consecutive catalytic runs. This is the first report of the application of mlc-SILP materials as catalysts in a reaction for the fixation of carbon dioxide. Rapid, parallel screening and comparison of the catalysts was performed by means of high-throughput experimentation.

The reaction between an excess of 1,4-bis(3-vinylimidazolium-1-yl) bromide and a mercaptopropyl-modified amorphous silica gel or ordered mesoporous silica SBA-15 in the presence of azobisisobutyronitrile (AIBN) afforded new materials, which have a high loading of imidazolium moieties. These materials, which contain a highly cross-linked polymeric network, have been denoted as multi-layered, covalently supported ionic liquid phase (mlc-SILP) and have been used as support for palladium catalysts containing a high loading of the metal (10 wt%). Such materials were characterized by several techniques (13C magic angle spinning nuclear magnetic resonance, the Brunauer–Emmett–Teller technique, small-angle X-ray scattering, X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy). The presence of a homogeneous distribution of palladium nanoparticles was established. The palladium catalysts displayed good activity allowing the synthesis of several biphenyl compounds in high yields working with only 0.1 mol% of palladium loading at mild temperatures (room temperature or 50 °C) in ethanol/water. Reactions carried out on a 10-mmol scale required only 10 mg of catalysts. Good recyclability was observed.