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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.

Understanding of polymorphism of organic semiconducting materials is the key to structural control of their electrical and mechanical properties. Motivated by the ambipolar n-type charge transport and electroluminescence of thienopyrrolyldione end-capped oligothiophenes, here we studied the propensity of one representative to crystallize as different polymorphs which display distinctly different mechanically properties. The crystal structures of the two polymorphs (denoted "α" and "β") of the material, 2,2′-(2,2′-thiophene-5,5′-diyl)bis(5-butyl-5H-thieno[2,3-c]pyrrole-4,6)-dione (C4-NT3N), were determined. In the α phase, the molecules interact strongly by Ï-stacking, forming columns which are bonded via C-H-O and chalcogen bonds, and this packing is consistent with the elastic behavior observed with the crystals. Instead, the β phase has the molecules aligned along their core forming layers. While the molecules interact strongly within the layers, they are practically unbound between the layers. The presence of slip planes in this form explains the plastic deformation induced by applying a force perpendicular to the (001). The thermal behavior and the enantiotropic relationship of the polymorphs are reported.

Defect-rich graphene oxide (dGO) was used as sorbent for organic contaminants of emerging concern in tap water, including drugs and dyes, and the performance compared to those of lower-defects graphene types. The role of holes and carbonyl- carboxylic groups on graphene nanosheets surface on the adsorption mechanism and efficiency was investigated. dGO showed enhanced adsorption capacity toward two fluoroquinolone antibiotics (ofloxacin, OFLOX, and ciprofloxacin, CIPRO) in tap water with a maximum capacity of 650 mg/g, compared to 204 mg/g for Hummers derived commercial GO (hGO) and 125 mg/g for less defected Brodie derived GO (bGO) for OFLOX. The role of defects on the selective adsorption of OFLOX was also modelled by MD simulations, highlighting a mechanism mainly driven by the shape complementarity between the graphene holes and the molecules. Adsorption isotherms revealed different adsorption model for dGO, with a Langmuir fitting for dGO and BET fitting for all the other investigated samples. The maximum adsorption capacity of dGO for OFLOX was about six times higher than that of Granular Activated Carbon (95 mg/g), the industrial adsorption standard technology. Finally, it was also demonstrated that dGO can be recovered from treated water by ultrafiltration, this preventing secondary contamination risks and enabling safe use of graphene nanosheets for water purification.

We report on the investigation of the influence of the molecular packing and film morphology on the field-effect charge mobility in 2,3-thienoimide-based oligothiophenes semiconductors (Cn-NT4N). Organic field-effect transistors are realized by implementing both vacuum and solution methods in order to control the solid-state phase of the active layer. Thermal sublimation in a high vacuum chamber and supersonic molecular beam deposition were used as vacuum-based fabrication approaches for preparing thin films, while lithographically controlled wetting was used, as a solution-deposition technique, for the fabrication of the microstructured films. Thermal sublimation leads to thin films with a phase packing showing ambipolar behaviour, while supersonic molecular beam deposition enables, by varying the deposition rate, the formation of two different crystal phases, showing ambipolar and unipolar field-effect behaviours. On the other hand, lithographically controlled wetting enables the formation of Cn-NT4N microstructured active layers and their implementation in field-effect transistors.

Thienopyrrole-dione (TI) end capped materials have recently emerged as polymorphic molecular semiconductors suitable as active layers of ambipolar light emitting transistors, photovoltaic cells and time temperature integrator devices. Here, we report the synthesis of a new derivative, namely 2,2′-([2,2′-bithiophene]-5,5′-diyl)bis(5-octyl-4-phenyl-4H-thieno[2,3-c]pyrrol-6(5H)-one) (R-NT4N), having monoreduced TI moiety (R-TI) end groups. Ring opening of the TI moiety by Grignard reagent addition followed by one-pot reduction/ring closure by triethylsilane afforded the R-TI precursor that was then exploited for the preparation of the target R-NT4N compound. Investigation of the fluorescence properties of thin films, as a function of the processing conditions, showed that different from all the other TI derivatives so far reported, R-NT4N exhibits linearly polarized fluorescent microstructures. Combined micro-Raman and confocal laser-scanning fluorescence microscopies on lithographically controlled wetting (LCW) patterned R-NT4N films allowed us to correlate the emission polarization directions with the microcrystal structures.