Assunta Marrocchi

Università degli Studi di Perugia | UNIPG · Department of Chemistry, Biology and Biotechnology

Organic semiconductors hold the promise of simple, large area solution deposition, low thermal budgets as well as compatibility with flexible substrates, thus emerging as viable alternatives for cost-effective (opto)-electronic devices. In this study, we report the optimized synthesis and characterization of a helically shaped polycyclic aromatic c...

"Sustainable Strategies in Organic Electronics reviews green materials and devices, sustainable processes in electronics, and the reuse, recycling and degradation of devices. Topics addressed include large-scale synthesis and fabrication of safe device materials processes that neither use toxic reagents, solvents or produce toxic by-products. Emerg...

Alkyne-containing organic semiconductors are once again becoming the subject of intense research focus, and recent advances have significantly enhanced their performance in optoelectronics. This perspective focuses on the results achieved...

The use of hydrogen at high-pressure is associated with major safety concerns, storage, and high cost. Therefore, the development of reductive chemical processes based on the use of low-pressure hydrogen is very attractive in view of an industrial-scale application. This perspective focuses on the most representative studies reported until 2021 dea...

The use of inhibition chemicals holds the prospect of an efficient strategy to control crystallization in porous materials, thereby potentially contributing to the prevention or mitigation of the salt decay phenomenon in modern as well as historical building materials in a more sustainable manner. In this review, we first provide an essential backg...

Two new benzo[b]thieno[2,3-d]thiophene (BTT) derivatives, 2-(benzo[b]thiophen-5-yl)benzo[b]thieno[2,3-d]thiophene (compound 2), and 2-(benzo[b]thieno[2,3-d]thiophene-2yl)dibenzo[b,d]thiophene (compound 3) have been synthesized and utilized as solution-processable small molecular organic semiconductors for organic field-effect transistors (OFETs). T...

The past decade has marked a renewed interest in borazines and BN‐doped polycyclic aromatic hydrocarbons. This is predominantly because of new advances that have highlighted their potential in various applications, including gas separation and storage, organic (opto)electronics, catalysis, and as supramolecular systems. This review gives a critical...

By exploiting the combined use of a heterogeneous recyclable palladium(II)-bis(N-heterocyclic carbene) catalyst and cyclopentyl methyl ether (CPME) as a convenient recoverable safer reaction medium, an effective waste-minimized approach has been developed for the intramolecular Pd-catalyzed C(sp3)-H activation of methyl pyrrole derivatives. This sy...

In this work, we explored the effect of solution-shearing processing parameters, coating speed and substrate temperature, on the electrical properties of solution-processed organic field-effect transistors (OFETs) based on 2-decyl-7-phenyl[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-C10) when green solvents are used. Organic semiconductor thin f...

Bio-based glycerol and aldehydes have been valorised by acetalization reaction over novel macroporous sulfonated polystyrene-type resins (MR-SP20-SO3H and MR-SP50-SO3H). The influence of reactants molar ratio, catalyst amount, temperature, and reaction time on the activity and selectivity to acetals have been investigated. Results showed that MR-SP...

Liquid organic hydrogen carriers (LOHCs) are attractive materials for their ability to generate in situ hydrogen that may be directly used to produce target biofuel precursors, fuels or fuel additives. Indeed, the replacement of fossil feedstock is an urgent necessity for shifting toward a carbon neutral energy economy. Several desired chemicals an...

In this study, we report strong experimental evidence for singlet fission (SF) in a new class of fluorene-based molecules, exhibiting two-branched donor-acceptor structures. The time-resolved spectroscopic results disclose ultrafast formation of a double triplet state (occurring in few picoseconds) and efficient triplet exciton separation (up to 14...

A brewers’ spent grain (BSG) based dielectric material was used in organic field-effect transistors (OFETs). The fabricated devices showed a maximum hole mobility of 2.30 cm ² V ⁻¹ s ⁻¹ .

In the trends of ever-growing worldwide interest for the environment/health and the corresponding legal regulations, there have been various studies to replace toxic halogenated/aromatic hydrocarbon organic solvents commonly used in the solution-processing of organic semiconductors (OSCs) with more sustainable green solvents. In this paper, we fabr...

Herein we report a simple protocol for the valorisation of a common urban biowaste. The lignocellulosic biomass obtained after the pre-treatment of pine needle urban waste is efficiently transformed into a low-cost support (PiNe) for the immobilization of Pd nanoparticles. The final Pd/PiNe heterogeneous catalyst features a small particle size (4.5...

Salt inhibitors have been receiving increasing attention as potential innovative systems to counteract salt damage by preventing crystallisation of the salts within the natural stone structure—and related disruptive action—of built heritage. Especially, we focus on biomass-derived inhibitor systems featuring complete solubility in water or alcohol...

In this study, we explored the effect of binary solvent system based on green solvent additives to form pre-aggregated solution and solution-processed organic semiconductor films for organic field-effect transistors (OFETs)...

Materials chemistry has been one of the most talked-about areas of materials research over the past decades [...]

Organic electronic FAB factories are hard-pressed due to the current regulatory requirements which restrict (or ban) the use of hazardous solvents; on the other hand, toxic halogenated (or aromatic hydrocarbon) solvents have been the most preferred processing options to date, since they typically enable ideal performance. In this review, we specifi...

The synthesis and a comprehensive characterization of the excited state properties of five N,N′-substituted indigo (Ind) derivatives (acetyl-, benzoyl-, methoxybenzoyl-, nitrobenzoyl- and chlorobenzoyl-) was undertaken in various solvents and temperatures. In the excited state, rotation around the central double bond was found with N,N′-diacetylind...

In this study, we explored a wide range of green solvents to process the semiconductor layer TIPS-PEN (6,13-bis(triisopropylsilylethynyl)pentacene), as well as to demonstrate potential generality, several p- and n-type organic semiconductors, for the fabrication of organic thin-film transistors (OTFTs). Our data demonstrate that several solvent opt...

In recent years, ventilation of indoor environment became relevant in the design of well-insulated buildings; with the aim of fulfilling energy saving requirements, new building mechanical ventilation systems have been developed to guarantee heat recovery. The most common heat recovery systems used in air conditioning systems permit only heat recov...

Formic acid is a main product from biomass-derived carbohydrates and is attracting ever more attention as a sustainable hydrogen source, owing to its high volumetric hydrogen density of 53 g of H2 per liter. In this review, we give an overview of the formic acid mediated transformations of biomass-based feedstocks into added-value products, includi...

The principles of Green Chemistry aim to improve the sustainability of chemical processes and reduce the generation of hazardous substances. There has been great growth in the field over the past few years and the number of research groups working in this area is still increasing. Now one of the biggest challenges is to embed the Green Chemistry id...

The influence of torsional disorder around the ethynyl π-bridges of a linear D-π-A-π-D molecule on the nature of its S1 excited state was investigated using ultrafast time-resolved infrared spectroscopy. By tuning the pump wavelength throughout the S1←S0 absorption band, subpopulations with different extents of asymmetry could be excited. In non-po...

A resin-bound 1,2,4-triazolium ionic tag has been used as support for the preparation of solid palladium nanoparticles (Pd(0)-POLI-TAG-Pd). Owing to the pincer-type architecture of the triazolium ligand, the stabilization of a high amount of palladium nanoparticles (16 wt%) has been possible. The catalytic system has been fully characterized and us...

The [PdCl4]2− palladium complex has been immobilized on a polystyrene-type resin loaded with pincer-type imidazolium ionic tag binding sites. The catalytic system (Pd(II)-POLI-TAG) has proved to be highly active in the definition of an efficient protocol for the Heck–Mizoroki coupling reaction under batch and flow conditions. Importantly, it is sho...

Transition‐metal catalyzed C−H functionalization reactions have progressed enormously, becoming a useful tool in organic synthesis and a practical alternative to well‐established methodologies. Very recently, research efforts have also been devoted to developing more sustainable C−H functionalization protocols, in order to increase their applicabil...

An effective flow protocol exploiting the features of a specifically designed solid catalytic system has been defined for the direct esterification of biomass-derived carboxylic acids with structurally diverse alcohols on...

Herein we report an efficient procedure for the C–H functionalization of 1,2,3-triazoles in continuous flow regime applied to a variety of functionalities and to the inter- or intramolecular versions of the process. The continuous-flow protocol is based on the use of an heterogeneous catalyst (Pd/C), a soluble organic base and GVL as reaction mediu...

In this investigation, we explored for the first time the use of cross-linked sulfonated poly (ether ether ketone) (SPEEK) membranes in the fabrication of enthalpy heat exchangers. SPEEK is very sensitive to changes in relative humidity, especially when featuring high degrees of sulfonation (DS), though a poor mechanical stability may be observed i...

In the last decade, transition‐metal catalyzed C‐H functionalization reactions have progressed enourmosly, becoming a useful tool in organic synthesis and a practibable alternative to well‐established methodologies. Very recently, research efforts have also been devoted to developing more sustainable C‐H functionalization protocols, in order to inc...

The drive toward greener process chemistry has stimulated the development of strong solid acids to replace traditional catalysts for efficient biodiesel production from free fatty acid (FFA) enriched biomass feedstocks. Notably, heterogeneous systems enable simple product isolation procedures and improve the catalyst recyclability. They may also be...

A novel polymer semiconductor based on squaric acid is successfully prepared through polycondensation reaction. Physicochemical properties of polysquaraine are explored by Fourier transform infrared (FT-IR) and ultraviolet-visible (UV-vis) absorption spectroscopy, thermogravimetric/modulated temperature differential scanning calorimetry (TGA/MTDSC)...

Green/Sustainable Chemistry is the scientific platform where chemists are contributing from different areas to develop modern and efficient processes aimed at minimizing the environmental impact of chemical production. To reach these goals scientists, from both academia and industry, need to strongly focus their fundamental and innovative research...

In this paper we propose a new mathematical model describing the effect of phosphocitrate (PC) on sodium sulphate crystallization inside bricks. This model describes salt and water transport, and crystal formation in a one dimensional symmetry. This is a preliminary study that takes into account mathematically the effects of inhibitors inside a por...

Given the wide utility of click-chemistry reactions for the preparation of simple moieties within large architecturally complex materials, this minireview article aims at surveying papers exploring their scope in the area of π-conjugated polymers for application in organic electronics to enable advanced functional properties.

Three quadrupolar D−π−A−π−D compounds, bearing alkoxy phenyls as mild electron donors and a benzothiadiazole (A), two benzothiadiazoles (B) or a benzothiadiazole linked to two thiophenes (C) as the acceptor units, are the object of this study. They proved to be efficient yellow/orange/red fluorophores, respectively, with fluorescence being their pr...

The peculiar photobehaviour of a symmetrical arylenevinylene anthracene derivative bearing mild electron donors (alkoxy groups) at the sides of its structure has been fully comprehended through this study. An investigation into the effect of solvent polarity and temperature on the stationary fluorescence spectrum allowed a clear dual emission to be...

The most effective synthetic methodologies currently employed for producing polymeric semiconductors are affected by cost, safety, and environmental issues which may seriously prevent their large-scale production. In this regard, the application of principles of green chemistry for the development of waste-minimized and cleaner synthetic approaches...

The temperature effect on the photophysical parameters of four acetylene-derivatives [bis(phenylethynyl)-anthracenes and -fluorenes with substituents of different electron acceptor efficiencies] has been investigated by absorption and emission spectroscopy, using stationary and pulsed (ns/fs resolution) techniques. The nature of the central nucleus...

A new protocol for the diasteroselective synthesis of pyrrolidin-2-ones 4−14 is presented. Aquivion PFSA effectively catalyzed the diasteroselective nitro-mannich/lactamization cascade reaction between the imine formed from aldehydes 1a−g and amines 2a−b with methyl 3-nitropropanoate 3. The use of flow conditions allow a very efficient waste minimi...

The spectroscopic and photophysical behavior of a series of six extended arylacetylenes and one 1,3-diyne derivative was studied in solvents of different polarity to gain insight into the relationships between molecular architecture and optical/photophysical properties. The radiative decay channel was revealed to be the most important one for all t...

In this paper we propose a new mathematical model describing the effect of phosphocitrate (PC) on sodium sulphate crystallization inside bricks. This model describes salt and water transport, and crystal formation in a one dimensional symmetry. This is the first study that takes into account mathematically the effects of inhibitors inside a porous...

gamma-Valerolactone (GVL) can be used as an efficient and practical alternative to the banned and commonly used dipolar aprotic solvents. In this contribution GVL has been used as a non-toxic, biodegradable, biomass-derived medium, for the definition of a simple and general protocol for the Sonogashira cross-coupling reaction. The chemical efficien...

The first catalytic approach to the nucleophilic addition of silyl ketene acetals 2 to epoxides 1 is reported. The defined protocol is metal-free using tetrabutylammonioum fluoride as the catalyst. It works in a very efficient manner under solvent-free conditions (SolFC) allowing γ-lactones 3 to be directly obtained with high regioselectivities and...

Sun simulators are employed to test the performance of photovoltaic (PV) devices, according to the standard International Electrotechnical Commission (IEC) 61215. Economical and technical analysis show that PV manufacturers need to integrate Sun simulators in the production process and, in particular, at the end of the production chain in order...

gamma-Valerolactone (GVL) is an excellent reaction medium, derived from biomasses, which can replace classic dipolar aprotic media such as DMF or NMP. In this contribution, we have investigated the use of GVL in the palladium-catalyzed Heck reaction and have accessed the clean synthesis of several small molecules. Furthermore, we optimized a GVL-ba...

Green chemistry and flow chemistry are ideal partners for accessing novel chemical spaces and define highly efficient synthetic tools. In this review article contributions have been selected according to the advantages offered in terms of features that are not immediately related to classic green metrics such as minimization of reaction time, optim...

In this contribution we report the photophysical study of three organic blend systems comprising [60]PCBM along with different combinations of five extended semiconducting arylacetylenes, i.e. p-[(2-{[m,p-didodecyloxyphenyl]ethynyl}-7-fluorenyl)ethynyl]benzonitrile, 4,7-bis(5-{[m,p-bis(hexyloxy)phenyl]ethynyl}thien-2-yl)-2,1,3-benzothiadiazole, 9,1...

Owing to the high viscosity of the materials involved, mixing is often a critical step when processing polymer-modified bitumen, directly influencing the microstructure and the stability of final products. We provide experimental evidence suggesting that laminar chaotic advection may prove a valuable strategy for obtaining a homogeneous and finely...

Over the last two decades, ever increasing interest has been focused on π-conjugated triple-bond-containing systems, namely, (poly)aryl acetylenes, as a very promising class of semiconducting materials, owing to the availability of flexible/efficient synthetic protocols and the new conception of their conformational and steric advantages. In this r...

We report the photobehaviour of a series of eight structurally related arylacetylene derivatives, in solution as well as in pristine and PC61BM blended thin- films. The formation of both H- and J-aggregates in the solid state have been demonstrated, and, interestingly, an energy transfer from H-aggregates or/and from residual "unstacked" molecules...

In the search for efficient and polymeric supports for organic bases to be used in environmentally friendly media and conditions, novel polystyrene-bound 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) has been prepared and characterized. Their catalytic properties have been tested in the Michael additions of 4-hydroxycoumarin to α,β-unsaturated ketones...

Surface immobilization of conjugated polymers to functionalized surfaces by their end-point to afford polymer brushes would be an interesting alternative for high-performance, long-term operation organic (opto)electronics, possibly helping charge injection and charge transport processes which are crucial for many devices. In this review we focus on...

Herein we have reported some examples of our research devoted to the development of an efficient sustainable chemistry. We believe that academic and industrial approaches should converge towards innovative but also cost and environmentally effective solutions. We are pursuing a fully green approach to novel organic semiconductors able to exploit so...

Salt crystallization in porous materials constitutes one of the major causes of decay of buildings/archaeological sites in a wide range of environments. Desalination is among the most common methodologies of conservative treatment for salt decay. However, classical desalination techniques might be not suitable for long-term conservation. During the...

We report here the first study illustrating the attraction of fabricating solution-processed small molecule field-effect transistors and bulk heterojunction solar cells with semiconductors prepared using new sustainable synthetic procedures which minimize waste per kg of product (E-factor minimization).

Poly(3-hexylthiophene) (P3HT) remains of significant importance as a prototypical benchmark hole conductor material in Organic Photovoltaics (OPVs). In this review we discuss synthetic strategies to P3HT, particularly focusing on those leading to the regioregular form and discussing key physical and morphological properties. Finally, a survey and a...

Two flavors of π: Semiconducting π-conjugated polymers may open new opportunities for the fabrication of ecofriendly, inexpensive optoelectronic devices. These materials can be prepared by direct arylation polycondensation, a straightforward approach that generates little waste and no toxic by-products.

Neue Wege zu umweltfreundlichen und kostengünstigen optoelektronischen Bauteilen können halbleitende π‐konjugierte Polymere eröffnen. Diese Materialien sind durch direkte arylierende Polykondensation zugänglich, einem unkomplizierten Ansatz, der wenig Abfall und keine toxischen Begleitprodukte liefert.

In the search for molecules for organic photonics and electronics, several strategies have been used to modulate physical and chemical properties of [2.2]paracyclophane derivatives by sequential functionalization of their three-dimensional cores. This review summarizes the major design and synthetic strategies for tuning paracyclophane-containing s...

Detailed investigations by time-resolved transient absorption and fluorescence spectroscopies with nano- and femtosecond time resolutions are carried out with the aim of characterising the lowest excited singlet and triplet states of three ethynyl fluorenes (1-3) and three ethynyl anthracenes (4-6) in solvents of different polarity. The solvent is...

Although its intriguing features, such as uniform functionalization through the entire beads and a very high-loading capacity are suitable candidates for solid-phase synthesis and reagent-scavenging, the use of Rasta resin as support for organocatalysis has been little explored. In this contribution, Rasta polymer has been used to preparation of hi...

Blends of chemically readily accessible, small-molecular arylacetylene derivatives with poly(vinylidene fluoride) (PVDF) are presented that allow reliable solution processing of field-effect transistor (FET) architectures with electronic characteristics comparable to those of the neat semiconductors. We demonstrate that having the chemical means an...

Two series of soluble and thermally stable asymmetric arylacetylene derivatives bearing a fluorene (Fl-Xs) or an anthracene (An-Xs) core unit and end-substituted with different electronically active groups (X=NO2, CN, CHO and OR) were synthesized and characterized. The spectral and photophysical behaviour of these compounds was studied in two solve...

The synthesis and characterization of a new series of anthracene-based derivatives and their use as donors in bulk-heterojunction solar cells is reported. It is found that when using well-defined building blocks in constructing the chromophore, the donor molecular shape dramatically affects organic photovoltaic (OPV) performance in a previously unr...

Water has proved to be an excellent reaction medium for the definition of highly chemically-efficient and environmentallyfriendly synthetic processes. In several cases, by exploiting the unique properties of water it has been possible to realize more selective and efficient processes than those performed in organic media, including the ring-opening...

In this contribution we have reported about bi-component blends of readily accessible semiconducting molecular arylacetylenes with insulating high-density polyethylene (HDPE) and poly(vinylidene fluoride) (PVDF) that may exhibit electronic characteristics comparable to those of the neat semiconductors, as measured in field-effect transistors (FETs)