Organic- and Water-Soluble Aminoalkylsulfanyl Polythiophenes

Abstract

Six new aminoalkylsulfanyl polythiophenes (PTs), namely PTNHBoc, PTNMeBoc, PTNH2,PTNHMe, PTNMe2, and PTN+Me3, were synthesized. Four of them were obtained through Stille coupling, whereasPTNH2 and PTNHMe were obtained through deprotection via N-Boc precursors. The solubility changes goingfrom the protected amines to the quaternary ammonium salt. All the polymers are soluble in DMSO and DMF.PTNHBoc and PTNMeBoc are also soluble in CHCl3, CH2Cl2, THF, and DMPU; PTNH2 and PTNHMe aresoluble in CH3OH, whereas PTNMe2 and PTN+Me3 are soluble both in CH3OH and in H2O. These PTs show atendency toward microaggregation in solution that does not represent an obstacle to their solubility. NMR, UV-vis,and XRD results prove that they are able to reach very high conjugation lengths and ordered conformations, notonly in the solid state but also in solutions of good solvents

Colloids of semiconducting polymers for high-performance, environment-friendly polymer field effect transistors

“…Note that the mobility values obtained from the BA-based PFETs are quite close to the realistic minimum requirement for driving FETs of commercial organic light emitting diodes [20]. To the best of our knowledge, the present mobility values are the highest among those of PFETs processed using relatively green solvents [5][6][7].…”

“…In the field of semiconducting polymers, however, efforts to fabricate polymer colloids to meet the trend toward greener polymer technologies have been limited [5][6][7]. This can be attributed in part to the fact that the colloids of semiconducting polymers usually exhibit very low charge carrier mobility.…”

Polymers with Alkylsulfanyl Side Chains for Bulk Heterojunction Solar Cells: Toward a Greener Strategy

“…The symmetry of the monomer involved in P3 excludes the presence of structurally different alkyl chains and, at first, we assigned the deshielded alkysulfanyl chain and the shielded alkoxy chain to those of the terminal units, by comparison with the chemical shift of the monomers, whereas the shielded alkylsulfanyl chains were assigned to chains trapped in π‐stacked aggregates. To confirm these assignments, we used NOESY, that is another valuable experiment to highlight the presence of aggregates . In principle, the effect of π‐stack aggregation could be observed directly as a broad hump, highfield shifted with respect to the aromatic signals, in the 1D 1 H NMR spectrum and sometimes, as for P3 , this broad hump is low and can be missed.…”

“…To confirm these assignments, we used NOESY, that is another valuable experiment to highlight the presence of aggregates. [19,21,22,28,29] In principle, the effect of π-stack aggregation could be observed directly as a broad hump, highfield shifted with respect to the aromatic signals, in the 1D 1 H NMR spectrum and sometimes, as for P3, this broad hump is low and can be missed. The hypothesis of π-stacking is confirmed when several types of alkyl chains, not attributable to regiochemically different chains, are detected through TOCSY and when broad and high-field shifted correlations between aliphatic and aromatic protons are detected in the NOESY experiment ( Figure S3, Supporting Information).…”

Alcohol as a Processing Solvent of Polymeric Semiconductors to Fabricate Environmentally Benign and High Performance Polymer Field Effect Transistors

“…Accordingly, several methodologies have been tried that can enable the processing of polymeric semiconductors in “greener” solvents to realize environmentally benign PFETs . For example, in 2009, Lu and co‐workers reported the synthesis of an ethanol‐soluble polythiophene derivative with oxetane substitution in the side chain with a mobility of ≈10 −3 cm 2 V −1 s −1 in a PFET, which can be viewed as a target value for the highest mobility from water or ethanol‐processed PFETs.…”