Alberto Zanelli

Italian National Research Council | CNR · Institute for Organic Syntheses and Photoreactivity ISOF

In this study, we introduce a novel family of symmetrical thiophene‐based small molecules with a Donor‐Acceptor‐Donor structure. These compounds feature three different acceptor units: benzo[c][1,2,5]thiadiazole (Bz), thieno[3,4‐b]pyrazine (Pz), and thieno[1,2,5]thiadiazole (Tz), coupled with electron donor units based on a carbazole‐thiophene deri...

The growing interest in energy storage devices, both batteries and capacitors, could lead to the improvement of electrochemical properties such as extended charge/discharge cycles, high specific capacitance, and power density. Furthermore, the use of easily available raw materials for the production of carbon electrodes has attracted interest due t...

Three new ionic polythiophene derivatives, soluble in polar solvents, are synthesized with good yields using simple, low‐cost, and straightforward procedures. They are investigated as interfacial cationic conjugated polyelectrolyte (CPE) layers for halogen‐free bulk heterojunction (BHJ) polymeric solar cells, based on a water‐soluble electron‐donor...

Four new conjugated polymers alternating benzothiadiazole units and thiophene moieties functionalized with ionic phosphonium or sulfonic acid salts in the side chains were synthesized by a postfunctionalization approach of polymeric precursors. The introduction of ionic groups makes the conjugated polymers soluble in water and/or polar solvents, al...

Protein-based microfibers are biomaterials of paramount importance in materials science, nanotechnology, and medicine. Here we describe the spontaneous in situ formation and secretion of nanostructured protein microfibers in 2D and 3D cell cultures of 3T3 fibroblasts and B104 neuroblastoma cells upon treatment with a micromolar solution of either u...

The exponentially growing market of electrochemical energy storage devices requires substitution of flammable, volatile, and toxic electrolytes. The use of Water in salt solutions (WiSE) regarded as green electrolyte might be of interest thanks to an association of key features such as high safety, low cost, wide electrochemical stability, and high...

Nowadays communication skills are essential for the successful future career of undergraduate students, as well as to develop a mindset able to face new challenges linked to a sustainable development and to adopt sustainable strategies with respect to finite resources on Earth allowing the transition to the circular economy (CE) model. Here we pres...

Here is reported an expedient synthesis implementing enabling technologies of a family of thiophene-based heptamers alternating electron donor (D) and acceptor (A) units in a D–A′–D–A–D–A′–D sequence. The nature of the peripheral A groups (benzothiadiazole vs. thienopyrrole-dione vs. thiophene-S,S-dioxide) and the strength of the donor units (alkyl...

The electronic, optical, and redox properties of thiophene-based materials have made them pivotal in nanoscience and nanotechnology. However, the exploitation of oligothiophenes in photodynamic therapy is hindered by their intrinsic hydrophobicity that lowers their biocompatibility and availability in water environments. Here, we developed human se...

The exponentially growing market of electrochemical energy storage devices requires substitution of flammable, volatile, and toxic electrolytes. The use of Water in salt solutions (WiSE) regarded as green electrolyte might be of interest thanks to an association of key features such as high safety, low cost, wide electrochemical stability, and high...

Today some rawRaw materialsmaterialsMaterials (RMs) have become essential in the manufacturing of common goods and technologies (i.e., mobile phones, computers, automobiles). Readily accessible rawRaw materialsmaterialsMaterials, such as rare earthRare earthselementsRare earth elements (REEs), indiumIndium, neodymium, and others are important to in...

Main chain conjugated linear polymers, constituted by alternating electron-donor (D) and -acceptor (A) moieties, have been prepared with the aim of testing their performances as photoactive components in single material organic solar cells (SMOSCs). The D moiety is constituted by bithiophene co-units bearing in the position 3 of the thiophene ring...

Oligothiophenes are pi-conjugated semiconducting and fluorescent molecules whose self-assembly properties are widely investigated for application in organic electronics, optoelectronics, biophotonics and sensing. We report here an approach to the preparation of crystalline oli-gothiophene nano/micro-fibers based on the use of a sulfur overrich quat...

One of the key challenges in materials science is to control the properties of a material by directing its supramolecular arrangement. Here, we show that through nanoprecipitation method Iridium complexes, such as FIrpic, Ir-PPY and Ir-MDQ, can be organized into crystalline and phosphorescent nanoparticles allowing to thoroughly modify their functi...

In this work, the fluorenone molecule was symmetrically difunctionalised in the 3,6-positions with four different arylamine moieties. Using slow evaporation, the four fluorenone derivatives (FO1-4) exhibit good ability to arrange into microstructures in the solid state. The electronic and steric effects of arylamine substituents influence both opti...

Oligothiophenes are π‐conjugated semiconducting and fluorescent molecules whose self‐assembly properties are widely investigated for application in organic electronics, optoelectronics, biophotonics, and sensing. Here an approach to the preparation of crystalline oligothiophene nano/microfibers is reported based on the use of a “sulfur overrich” qu...

Regioregular HH-TT poly(3,3′-thioalkylbithiophene)s-bearing branched or linear alkyl side-chain substituents (PT2SR) have been synthesized and characterized to investigate their behavior, when used as electron-donor components in blend with a fullerene derivative [[6,6]-phenyl-C61-butyric acid methyl ester (PCBM)] as an electron acceptor, in air-pr...

Many emerging contaminants pass through conventional wastewater treatment plants, contaminating surface and drinking water. The implementation of advanced oxidation processes in existing plants for emerging contaminant remediation is one of the challenges for the enhancement of water quality in the industrialised countries. This paper reports on th...

The performances of remediation processes initiated by ionizing radiation on ofloxacin are investigated in ambient conditions. The effectiveness of the decomposition of ofloxacin has been assessed both by γ-rays and electron beam in various aqueous solutions differentiated by the dissolved gases (Air or oxygen saturated) and H2O2. By HPLC it is sho...

We describe the preparation of poly(3-hexylthiophene-S,S-dioxide) nanoparticles using Rozen’s reagent - HOF•CH3CN - either on poly(3-hexylthiophene) (P3HT) or on preformed P3HT nanoparticles (P3HT-NPs). In the latter case core-shell nanoparticles (P3HT@PTDO-NPs) are formed, as confirmed by X-ray Photoelectron Spectroscopy measurements indicating th...

A platform is described for the first time for the facile synthesis of oligo- and polythiophene-S-oxides and the corresponding -S,S-dioxides in short times, mild conditions, high yields. Employing ultrasound assistance, brominated thiophenes are selectively mono- or dioxygenated at room temperature. These building blocks are then combined with meta...

Highly soluble air-stable conjugated decamers and polymers (compounds 1-6) with alternating "sulfur-overrich" bis(3,4′-S-alkyl)-2,2′-bithiophenes as the donor units and 2,1,3-benzothiadiazoles as the acceptor units were designed and expediently synthesized with the aid of microwave and ultrasound enabling technologies. Solid-state cyclovoltammetry...

Fullerene-based tetrads, triads, and dyads are presented in which [60]fulleropyrrolidine synthons are linked to an oligo(p-phenyleneethynylene) antenna at the nitrogen atom and to electron-donor phenothiazine (PTZ) and/or ferrocene (Fc) moieties at the α carbon of the pyrrolidine cycle through an acetylene spacer. Cyclic voltammetry and UV/ Vis abs...

2,3-Thieno(bis)imide (N) ended oligomers are emerging as valuable molecular materials for application in organic electronics. Here, we report the synthesis and characterization of three new 2,3-thieno(bis)imide ended oligothiophenes (T) bearing unsaturated ethylene (E), azomethine (I) and ethinyl (A) inner bridges (NTE, NTI and NTA respectively). T...

Polymorphic crystalline microfibers from an achiral octithiophene with one S-hexyl substituent per ring are separately and reproducibly grown with the same characteristics on various solid surfaces, including the interdigitated electrodes/SiO2 surface of a bottomcontact field-effect transistor. The arrangement of the same molecule in two diverse su...

A facile and efficient method based on electrochemistry for the production of graphene-based materials for electronics is demonstrated. Uncharged acetonitrile molecules are intercalated in graphite by electrochemical treatment, owing to the synergic action of perchlorate ions dissolved in acetonitrile. Then, acetonitrile molecules are decomposed wi...

The synthesis of two new thieno(bis)imide (TBI, N) end functionalized oligothiophene semiconductors is reported. In particular, trimer (NT3N) and pentamer (NT5N) have been synthesized and characterized. Two different synthetic approaches for their preparation were tested and compared namely conventional Stille cross coupling and direct arylation re...

A dyad () made of a linear () and an angular () perylene biscarboximide is synthesized and its spectroscopic, electrochemical and photophysical properties investigated in solvents of various polarity. is characterized by a high intersystem crossing. The spectroscopy and electrochemistry data point to a modest electronic coupling. LUMO-LUMO electron...

The present paper deals with the remediation of water polluted by relatively poor biodegradable pharmaceuticals and personal care products. Specifically here we exploit the ability of the EB method to achieve their mineralization in atmospheric conditions at room temperature. Also we aim to i) explore and compare the performances of the EB system i...

The present study reports the photodegradation of surfactants, facing the issue in two steps. Initially, anionic, non ionic, and cationic surfactants have been treated separately. The second step performed the treatment of second rinsing water from laundry machine. This effluent contained traces of standard dirt, anionic, non ionic, and other deter...

International Trade Fair of Material & Energy Recovery and Sustainable Development Advanced Oxidation Processes for the remediation of water contaminated by emerging pollutants SUMMARY The destruction of selected emerging pollutants (pharmaceuticals and UV filters) in spiked water has been achieved by means of Advanced Oxidation Processes. The ener...

The different exfoliation routes of graphite to produce graphene by sonication in solvent, chemical oxidation and electrochemical oxidation are compared. The exfoliation process and roughening of a flat graphite substrate is directly visualized at the nanoscale by scanning probe and electron microscopy. The etching damage in graphite and the proper...

The synthesis and characterization of two thieno(bis)imide based n-type semiconductors with electron mobilities of up to 0.3 cm(2) V(-1) s(-1) are described. The relationships between the electronic features of the π-inner core and the functional properties of the new materials are also discussed.

A novel semiconducting benzothiadiazole (BTZ)-thiophene (T) co-oligomer having an unprecedented BTZ-T alternated motif has been synthesized and self-assembled into micrometer sized fibers by simple solution processing. The electrical properties of these low-dimensional architectures have been characterized by integrating them in an organic field-ef...

We describe the expedient synthesis of regioregular thiophene hexadecamers head-to-head (hh) substituted with hexyl and hexylthio grous. The synthesis was carried out by means of a sequence of ultrasound-assisted selective monobrominations and microwave-assisted Suzuki reactions using 4,4,5,5-tetramethyl-1,3,2-dioxaborolane in THF:water. The hexade...

A detailed photophysical characterization of a couple of new perylene imide derivatives, a carboxylic trisimide PIx, and an asymmetrically substituted carboxylic bisimide PIa is presented. PIx and PIa have the lowest singlet excited state just below 2.6 eV. The dyes are remarkably fluorescent (ϕ(f) = 0.37 ± 0.03 for PIa and ϕ(f) = 0.58 ± 0.04 for P...

Summary The destruction of selected emerging pollutants (pharmaceuticals and UV filters) in spiked water has been achieved by means of Advanced Oxidation Processes. These processes can be generated by irradiating water solutions with UV-light, g-rays, electron-beams, or even ultrasounds. The energy transmitted with these processes interacts mainly...

The design, synthesis and structure-property investigation of a new thienopyrrolyl dione substituted oligothiophene material showing reduced band gap energy, low lying LUMO energy level and ambipolar semiconducting behaviour is described.

Here, we describe a simple approach to fabricate graphene-based field-effect-transistors (FETs), starting from aqueous solutions of graphene-oxide (GO), processed entirely under ambient conditions. The process relies on the site-selective reduction of GO sheets deposited in between or on the surface of micro/nanoelectrodes. The same electrodes are...

The synthesis and characterization of a novel polythiophene substituted with a 2′-pentyloxy-5′-(1″′-oxooctyl) phenyl group (PPOPT) is reported. The bulk transport properties of thin films of PPOPT are investigated by admittance spectroscopy. The dramatic effect of the phenyl side chain on the mobility of positive carriers in films of PPOPT is descr...

Functional supramolecular architectures for bottom-up organic nano- and microtechnology are a high priority research topic. We discovered a new recognition algorithm, resulting from the combination of thioalkyl substituents and head-to-head regiochemistry of substitution, to induce the spontaneous self-assembly of sulfur overrich octathiophenes int...

Functional supramolecular architectures for bottom-up organic nano- and microtechnology are a high priority research topic. We discovered a new recognition algorithm, resulting from the combination of thioalkyl substituents and head-to-head regiochemistry of substitution, to induce the spontaneous self-assembly of sulfur overrich octathiophenes int...

We have demonstrated that PEO-based polymer electrolytes prepared by solvent-free procedures and with the addition of particle-size ceramic powder have very stable lithium interface properties - a very important feature for the development of successful lithium metal polymer batteries (LPBs). The results of cyclability tests at different charge-dis...

Transport of holes in a low band gap polyfluorene, APFO-Green6, was investigated by means of admittance spectroscopy in the modulation frequency range 1–10⁶ Hz . At room temperature, hole mobility of APFO-Green6 is dependent on the applied electric field, as commonly observed in disordered organic materials. The excess capacitance toward...

Newly synthesized thiophene (T) and benzothiadiazole (B) co-oligomers of different size, alternation motifs, and alkyl substitution types are reported. Combined spectroscopic data, electrochemical analysis, and theoretical calculations show that the insertion of a single electron-deficient B unit into the aromatic backbone strongly affects the LUMO...

Novel inner-core dithienothiophene S-oxide and S,S-dioxide oligomers were designed and synthesized. The controlled oxidation at the central sulfur of the dithienothiophene core allows the combined tailoring of the HOMO-LUMO energies, thermal properties, and thin film morphology. Electrochemical measurements indicate that a marked decrease in electr...

Two chemiresistors based on two interpenetrating networks of a polymer and a polyelectrolyte have been characterized by impedance spectroscopy in 10 ethanol/cyclohexane blends to evaluate the feasibility of a sensor for the detection of ethanol into gasoline. The chemiresistors show high sensitivity, negligible hysteresis and non-linear temperature...

A series of arrays for light-driven charge separation is presented, in which perylene tetracarboxylic bisimide is the light-absorbing chromophore and electron acceptor, whereas isoxazolidines are colourless electron donors, the electron-releasing properties of which are increased with respect to the amino group by means of the alpha-effect. Charge...

Four dyads comprised of corrole and coumarin units have been synthesised. Three coumarincarboxaldehydes were synthesized and transformed into the corresponding trans-A(2)B-corroles by reaction with 5-(pentafluorophenyl)dipyrromethane. It has been proven that this type of direct condensation can lead to the corresponding corroles in moderate yields....

A hybrid [Pt((t)Bu(3)terpy)(C[triple bond]C-Ph-C(60))](+) complex (Pt-Fu) wherein a phosphorescent platinum center is linked to fullerene has been prepared using a copper(I)-promoted cross-coupling reaction. The electrochemical and spectroscopic properties were understood in light of the properties of the isolated building blocks and references com...

An interpenetrating polymer network based on poly(glycidyl methacrylate), diethylenetriamine, poly(4-vinylpyridine) and 1,4-dibromobutane has been investigated as sensitive material to build a sensor for the detection of ethanol in hydrocarbons. Preliminary tests have been carried out by impedance spectroscopy in ethanol/cyclohexane mixtures. The s...

DPY and DPE alkylenesulfanyl-bridged bithienyls were prepared by a highly effective ring-closing reaction via arylalkylsulfonium intermediate and used as inner cores in oligothiophenes. HOMO-LUMO energy levels, conformational flexibility, and intrinsic asymmetry of the cores are reflected in the electronic, film-forming, and thermal properties of t...

The electrical properties of polyelectrolytes depend on the water concentration of the environment. The behaviour of both conductance and capacitance caused by variations in relative humidity and temperature was investigated by impedance spectroscopy for humidity sensors based on an interpenetrated network of a polymer and a polyelectrolyte. The re...

A soluble, low-weight fraction of poly(alpha-vinyl,omega-n-hexyl-quaterthiophene), PT4Hex, having n-hexylquaterthiophenes as side-chain groups, is prepared by free-radical polymerization of alpha-vinyl,omega-n-hexyl-quaterthiophene and the corresponding properties compared to those of free di-n-hexylquaterthiophene (T4Hex). Optical analysis (absorp...

The synthesis, optical characterization and redox potentials of a branched polythiophene (V-PT), obtained by the Stille polycondensation of V-shaped 2,3-dibromo-benzo[b]thiophene-1,1-dioxide and 3,3-dimethyl-5,5′-tributylstannyl-2,2′-bithiophene, are reported. The branched shape favours the suppression of aggregation effects and the presence of the...

Films made of interpenetrated networks of a polymer and a polyelectrolyte, containing quaternary ammonium groups and bromide as counter-ion, and deposited onto interdigitated gold electrodes, were investigated by frequency response analysis as sensitive materials for the detection of water traces in organic solvents. Remarkable variations of both t...

The first trans-ruthenium complex trans-[Ru(DIP)2(MeOH)2][OTf]2 (1b, where DIP = 4,7-diphenyl-1,10-phenanthroline) incorporating a pi-extended ligand was prepared via two methods: either photolysis of cis-[Ru(DIP)2(OTf)2] in MeOH-Et(2)O or via crystallization from MeOH-Et(2)O in direct sunlight. The X-ray molecular structure of is reported and conf...

The paper reports on a characteristic property of electroactive materials bearing an electron-rich and an electron-poor moiety, known as charge trapping. As examples of materials that exhibit this phenomenon, films of poly(4,4″-dipentoxy-4′-(2,2′-dicyano)ethenyl-2,2′:5′,2″-terthiophene), poly(2,3-dihexylthieno[3,4-b]pyrazine) and a blend between a...

The sorption kinetic of water in interpenetrated networks of polyelectrolytes was investigated by monitoring the variation of impedance in the time. It was found that, while the sensitivity is better for the low dielectric solvents and for sensors based on the polyelectrolyte with lower ion density, the rate of the sensing kinetic is faster for the...

4-(Ferrocenylmethylidene)-4H-cyclopenta[2,1-b:3,4-b′]-dithiophene was electropolymerised both on indium-tin oxide and interdigitated gold electrodes. The optical and electrical characteristics of the polymer (PCPBTFC) were studied as a function of storage time and relative humidity. PCPBTFC showed both electronic and redox conductance and, in the p...

The kinetic behaviour of humidity sensors based on a cross-linked interpenetrated polyelectrolyte was investigated. Various parameters were changed in order to study their effect on the response to a humidity variation. The influence of the way of preparation of the polymer and of the sensing layer thickness are reported and discussed.

As part of our investigations into single-component organic solar cells, a symmetrical bis(styryl)benzene–fullerene dyad has been synthesized. An oxyethylene macrocyclic spacer, attached to meta-positions of side phenyl groups of bis(styryl)benzene, was linked to [60]fullerene through a synthesis based on the nucleophilic Bingel cyclopropanation of...

The conductance of interpenetrated polymer networks (IPNs) containing quaternary amino groups was studied in cyclohexane, toluene, ethyl ether, ethyl acetate, and tetrahydrofurane as a function of water content by electrochemical impedance spectroscopy. IPNs were then used as sensitive materials to detect water traces in organic solvents with promi...

The synthesis via the Stille coupling of a new family of oligomers derived from benzo[b]thiophene is reported. Owing to their branched molecular structure lacking any symmetry element, these compounds display a low tendency to crystallization and better film-forming properties than their linear counterparts. Spin-coated films show photoluminescence...

The kinetic behaviour of water sorption/de-sorption was investigated in polymer-salt complexes (PSC's) by observing the conductance variation over time. The conductance reached a steady state value through three processes with different kinetics occurring in different time regions. The three processes were singled out as, starting from the fastest...

New low-gap thiophene-based regular copolymers are produced by anodic coupling of 3,4-ethylenedioxythiophene-2,5-substituted thieno[3,4-b]pyrazine (TP), cyclopenta[2,1-b;3,4-b']dithiophen-4-one (CO), and 4-dicyanomethylene-4H-cyclopenta[2,1-b;3,4-b']dithiophene (CN). The copolymers are characterized by cyclic voltammetry, FTIR reflection-absorption...

The conductance of complexes between polyacetylene-based polymers and inorganic salts (dopants) was investigated in the presence of humidity as a function of the salt concentration. The conductance reaches a maximum value by increasing the doping level. The decrease of conductance observed for high-doping values is due to enhanced ion interactions....

Thiophene-based organic light-emitting diodes (OLEDs) were studied by an approach based on the replacement of the conventional linear structure of the oligothiophenes by a branched structure. The devices exhibiting a luminance of 10500 cd m-2 and electroluminescence (EL) efficiency of 0.45% in air were identified by substituting oligothiophenes wit...

3',4'-Dihexyl-4,4''-bis(pentyloxy)-2,2':5',2''-terthiophene was electrochemically polymerized on gold interdigitated electrodes to investigate the impedance variation of the polymer in the exposure to air/methane atmospheres. The higher sensitivity of poly[3',4'-dihexyl-4,4''-bis(pentyloxy)2,2';5',2''-terthiophene] (PHPT) to methane was observed at...

Per effettuare una valutazione rigorosa del rischio cancerogeno, occorre disporre di informazioni quantitative, oltre che sulla concentrazione e sui tempi di esposizione, anche sulla “potenza” dei vari agenti cancerogeni. Lo scopo di questo lavoro è individuare alcuni strumenti utili a dare una stima quantitativa della probabilità che si generino t...

Per effettuare una valutazione rigorosa del rischio cancerogeno, occorre disporre di informazioni quantitative, oltre che sulla concentrazione e sui tempi di esposizione, anche sulla “potenza” dei vari agenti cancerogeni. Lo scopo di questo lavoro è individuare alcuni strumenti utili a dare una stima quantitativa della probabilità che si generino t...

The cyclability performance of several composite polymer electrodes based on poly(thiophene) (pTh), poly(3-methylthiophene) (pMeT), and poly[3-(4-fluorophenyl)thiophene](pFPT), carbon, and a binder is reported. These composites were tested for use as positive and negative electrodes in supercapacitors for electric vehicle (EV) applications. The pTh...

Supercapacitors are devices for applications requiring high operating power levels, such as secondary power sources in electric vehicles (EVs) to provide peak power for acceleration and hill climbing. While electronically conducting polymers yield different redox supercapacitor configurations, devices with the n‐doped polymer as the negative electr...

The performance of several polymer electrolytes for lithium metal batteries for electric vehicle applications are reported. The best performing electrolyte is the composite PEO20LiCF3SO3-gamma LiAlO2, which was prepared by a solvent-free procedure. It showed coulombic efficiency values of the lithium deposition-stripping process of 94%-96%. Electro...