Tailoring, synthesis and structure-property relationships of 2,3-thienoimide based molecular materials

Organic molecular semiconductors are subject of intense research for their crucial role as key components of new generation low cost, flexible, and large area electronic devices such as displays, thin-film transistors, solar cells, sensors and logic circuits. In particular, small molecular thienoimide (TI) based materials are emerging as novel multifunctional materials combining a good processability together to ambipolar or n-type charge transport and electroluminescence at the solid state, thus enabling the fabrication of integrated devices like organic field effect transistors (OFETs) and light emitting transistor (OLETs). Given this peculiar combination of characteristics, they also constitute the ideal substrates for fundamental studies on the structure-property relationships in multifunctional molecular systems. In this scenario, this thesis work is focused on the synthesis of new thienoimide based materials with tunable optical, packing, morphology, charge transport and electroluminescence properties by following a fine molecular tailoring, thus optimizing their performances in device as well as investigating and enabling new applications. Investigation on their structure-property relationships has been carried out and in particular, the effect of different π-conjugated cores (heterocycles, length) and alkyl end chain (shape, length) changes have been studied, obtaining materials with enhanced electron transport capability end electroluminescence suitable for the realization of OFETs and single layer OLETs. Moreover, control on the polymorphic behaviour characterizing thienoimide materials has been reached by synthetic and post-synthetic methodologies, developing multifunctional materials from a single polymorphic compound. Finally, with the aim of synthesizing highly pure materials, simplifying the purification steps and avoiding organometallic residues, procedures based on direct arylation reactions replacing conventional cross-couplings have been investigated and applied to different classes of molecules, bearing thienoimidic core or ends, as well as thiophene and anthracene derivatives, validating this approach as a clean alternative for the synthesis of several molecular materials

Synthesis, size-dependent optoelectronic and charge transport properties of thieno(bis)imide end-substituted molecular semiconductors

n/

Graphene oxide doped polysulfone membrane adsorbers for the removal of organic contaminants from water

This work explored polysulfone (PS) – graphene oxide (GO) based porous membranes (PS-GO) as adsorber of seven selected organic contaminants of emerging concern (EOCs) including pharmaceuticals, personal care products, a dye and a surfactant from water. PS-GO was prepared by phase inversion method starting from a PS and GO mixture (5% w/w of GO). The porous PS-GO membranes showed asymmetric and highly porous micrometer sized pores on membrane top (diameter ≈20 μm) and bottom (diameter ≈2–5 μm) surfaces and tens of microns length finger like pores in the section. Nanomechanical mapping reveals patches of a stiffer material with Young modules comprised in the range 15–25 GPa, not present in PS pure membranes that are compatible with the presence of GO flakes on the membrane surfaces. PS-GO was immersed in EOCs spiked tap water and the adsorbance efficiency at different contact times and pH evaluated by HPLC analysis. Ofloxacin (OFLOX), benzophenone-3 (BP-3), rhodamine b (Rh), diclofenac (DCF) and triton X-100 (TRX) were removed with efficiency higher than 90% after 4 h treatments. Regeneration of PS-GO and reuse possibilities were demonstrated by washing with ethanol. The adsorption efficiencies toward OFLOX, Rh, DCF and carbamazepine (CBZ) were significantly higher than those of pure PS membrane. Moreover, PS-GO outperformed a commercial granular activated carbon (GAC) at low contact times and compared well at longer contact time for OFLOX, Rh, BP-3 and TRX suggesting the suitability of the newly introduced material for drinking water treatment

Biomimetic graphene for enhanced interaction with the external membrane of astrocytes

Graphene and graphene substrates display huge potential as material interfaces for devices and biomedical tools targeting the modulation or recovery of brain functionality. However, to be considered reliable neural interfaces, graphene-derived substrates should properly interact with astrocytes, favoring their growth and avoiding adverse gliotic reactions. Indeed, astrocytes are the most abundant cells in the human brain and they have a crucial physiological role to maintain its homeostasis and modulate synaptic transmission. In this work, we describe a new strategy based on the chemical modification of graphene oxide (GO) with a synthetic phospholipid (PL) to improve interaction of GO with brain astroglial cells. The PL moieties were grafted on GO sheets through polymeric brushes obtained by atom-transfer radical-polymerization (ATRP) between acryloyl-modified PL and GO nanosheets modified with a bromide initiator. The adhesion of primary rat cortical astrocytes on GO–PL substrates increased by about three times with respect to that on glass substrates coated with standard adhesion agents (i.e. poly-D-lysine, PDL) as well as with respect to that on non-functionalized GO. Moreover, we show that astrocytes seeded on GO–PL did not display significant gliotic reactivity, indicating that the material interface did not cause a detrimental inflammatory reaction when interacting with astroglial cells. Our results indicate that the reported biomimetic approach could be applied to neural prosthesis to improve cell colonization and avoid glial scar formation in brain implants. Additionally, improved adhesion could be extremely relevant in devices targeting neural cell sensing/modulation of physiological activity

Chemical design enables the control of conformational polymorphism in functional 2,3-thieno(bis)imide-ended materials

We report a successful chemical design strategy based on the even-odd alkyl end tailoring, which allows us to promote and control conformational polymorphism in single crystal and thin deposits of thienoimide-based molecular semiconductors (Cx-NT4N)

Synergic effect of unsaturated inner bridges and polymorphism for tuning the optoelectronic properties of 2,3-thieno(bis)imide based materials

2,3-Thieno(bis) imide (N) ended oligomers are emerging as valuable molecular materials for applications 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). The effect of the unsaturated bridge on the pi-conjugation extent, molecular conformation and overall aromaticity is related to the functional optoelectronic and morphological properties and compared to the properties of the linear analogue (NTT) with a bithiophene inner moiety. Optical spectroscopy and cyclovoltammetry analysis show a strong red shift of the absorption and an increased energy band gap on going from NTI and NTE to NTA. The HOMO level decreases in the order NTE > NTI > NTA. Moreover, while the LUMO of NTE and NTA have almost the same energy, NTI has a LUMO energy about 0.1 eV lower, likely due to the electron withdrawing effect of the azomethine moiety. Morphological investigation of solution cast thin deposits shows that the unsaturated bridges promote the formation of concomitant polymorphs with the simultaneous presence of microcrystals with different morphology and fluorescence properties. Moreover, irreversible conversion of one polymorph to the other was achieved by thermal treatments for NTA and NTE and by exploiting this feature, we realized a time temperature integrator (TTI) device based on NTE material. This device allowed to monitor temperature evolutions in the range between RT and 200 degrees C by means of a red to yellow fluorescence switch that was detectable by optical microscopy

Graphene oxide doped polysulfone membrane adsorbers for the removal of organic contaminants from water

This work explored polysulfone (PS) – graphene oxide (GO) based porous membranes (PS-GO) as adsorber of seven selected organic contaminants of emerging concern (EOCs) including pharmaceuticals, personal care products, a dye and a surfactant from water. PS-GO was prepared by phase inversion method starting from a PS and GO mixture (5% w/w of GO). The porous PS-GO membranes showed asymmetric and highly porous micrometer sized pores on membrane top (diameter ≈20 μm) and bottom (diameter ≈2–5 μm) surfaces and tens of microns length finger like pores in the section. Nanomechanical mapping reveals patches of a stiffer material with Young modules comprised in the range 15–25 GPa, not present in PS pure membranes that are compatible with the presence of GO flakes on the membrane surfaces. PS-GO was immersed in EOCs spiked tap water and the adsorbance efficiency at different contact times and pH evaluated by HPLC analysis. Ofloxacin (OFLOX), benzophenone-3 (BP-3), rhodamine b (Rh), diclofenac (DCF) and triton X-100 (TRX) were removed with efficiency higher than 90% after 4 h treatments. Regeneration of PS-GO and reuse possibilities were demonstrated by washing with ethanol. The adsorption efficiencies toward OFLOX, Rh, DCF and carbamazepine (CBZ) were significantly higher than those of pure PS membrane. Moreover, PS-GO outperformed a commercial granular activated carbon (GAC) at low contact times and compared well at longer contact time for OFLOX, Rh, BP-3 and TRX suggesting the suitability of the newly introduced material for drinking water treatment

Molecular Tailoring of New Thieno(bis)imide-Based Semiconductors for Single Layer Ambipolar Light Emitting Transistors

Organic molecular semiconductors are key components for a new generation of low cost, flexible, and large area electronic devices. In particular, ambipolar semiconductors endowed with electroluminescent properties have the potential to enable a photonic field-effect technology platform, whose key building blocks are the emerging organic light-emitting transistor (OLET) devices. To this aim, the design of innovative molecular configurations combining effective electrical and optical properties in the solid state is highly desirable. Here, we investigate the effect of the insertion of a thieno­(bis)­imide (TBI) moiety as end group in highly performing unipolar oligothiophene semiconductors on the packing, electrical, and optoelectronic properties of the resulting materials. We show that, regardless of the HOMO–LUMO energy, orbital distribution, and molecular packing pattern, a TBI end moiety switches unipolar and nonemissive oligothiophene semiconductors to ambipolar and electroluminescent materials. Remarkably, the newly developed materials enabled the fabrication of single layer molecular ambipolar OLETs with optical power comparable to that of the equivalent polymeric single layer devices