The synthesis, structural, electrochemical, and thin film electrical and electronic structural properties of a series of arylene diimide-oligothiophene n-type semiconductors are reported. This family of compounds allows analysis of the effects on thin film transistor performance of the following: (i) oligothiophene backbone catenation; (ii) naphthalenediimide vs perylenediimide core interchange; (iii) phenylene group introduction in the oligothiophene backbone. Electrochemical experiments indicate similar redox energetics for all members of this series, while thin film transistor measurements reveal markedly different charge transport performances. The highest electron mobility of 0.35 cm(2) V(-1) s(-1) is recorded for films of benzo[lmn]thieno[3',4':4,5]imidazo[2,1-b][3,8]phenanthroline-1,3,6(2H)-trione, 2-octyl (NDI-1T). Solution-processed field effect transistors were also fabricated and surprisingly exhibit electrical performances surpassing that of the vapor-deposited films in the case of isoquino[6',5',4':10,5,6]anthra[2,1,9-def]thieno[3',4':4,5]imidazo[2,1-a]isoquinoline-1,3,8(2H)-trione, 2-(1-heptyloctyl)-10,12-di-2-thienyl (PDI-3T).

Efficient post-functionalization of conductive polymer films was achieved by Cu(+)-catalyzed "click"-cycloaddition of novel poly(azidomethyl-EDOT) and various functionalized terminal alkynes under mild heterogeneous conditions with high conversion efficiencies.

We describe the synthesis and characterization of a novel poly(fluorene-alt-phenylene) substituted with perylenediimide (PDI) moieties as pendant groups. Cyclic voltammetry experiments show the amphoteric nature of the material, which combines the good electron donor ability of the polymeric chain with the acceptor properties of the pendant PDI moieties. Absorption spectroscopy suggests the presence of PDI aggregates, whereas the emission spectra show a strong emission quenching of both the polymeric backbone and the PDI units. Further investigation on the energy and/or electron-transfer processes involved is carried out by temperature-dependent excitation spectra and photoluminescence lifetimes. These studies show the presence of electron transfer not only from the electron donor polymeric chain to the pendant PDI units but also, and more remarkably, to PDI aggregates both in solution and in solid state, as is further confirmed by photoinduced absorption spectroscopy.

Poly(3,4-ethylenedioxythiophene) (PEDOT) is frequently used as a conducting layer in various applications, e.g., organic devices. However, the modification of the precursor 3,4-ethylenedioxythiophene (EDOT) has only very recently received some attention. Here, we report the efficient synthesis of chloromethyl-functionalized EDOT 3 which is a versatile intermediate to easily access functionalized EDOT derivatives and their corresponding PEDOTs bearing, e.g., electron acceptor groups. In this respect, novel EDOT derivatives 11-13 covalently functionalized with 9,10-anthraquinone (AQ), perylenetetracarboxylic diimide (PTCDI), and 11,11,12, have been synthesized and potentiodynamically electropolymerized. The redox properties of the new polymers P11-P13 were investigated, indicating that in the hybrid systems, both the PEDOT backbone and the acceptor moieties basically retain their individual properties. In the same line, optical spectra reveal the superimposition of the optical transitions of the individual π-systems.

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A peryleneamidine monoimide-fused terthiophene with a band gap of 1.4 eV has been synthesized. The donor-acceptor system can be electropolymerized to generate a functionalized polythiophene with a band gap of 0.9 eV and with ambipolar characteristics showing high electroactivity in both the p- and the n-doping process. This is the first example of a p-type conjugated polymer in direct conjugation with n-type perylenemonoimide moieties.

Novel poly(3,4-ethylenedioxythiophene) (PEDOT) polymers bearing imidazolium-ionic liquid moieties were synthesized by electrochemical polymerizations. For this purpose, new functional monomers were synthesized having an 3,4-ethylenedioxythiophene (EDOT) unit and an imidazolium-ionic liquid with different anions such as tetrafluoroborate (BF À 4 ), bis(trifluoromethane)sulfonimide ((CF 3 SO 2 ) 2 N À ), and hexafluorophosphate (PF À 6 ). Next, polymer films were obtained by electrochemical synthesis in dicholoromethane solutions. Obtained polymers were characterized, revealing the characteristics of PEDOT in terms of electrochemical and spectroelectrochemical properties, FTIR, 1 H NMR, and AFM microscopy. Interestingly, the hydrophobic character of electropolymerized films could be modified depending on the anion type. The hydrophobicity followed the trend PF À 6 [ (CF 3 SO 2 ) 2 N À [ BF À 4 [ pure PEDOT as determined by water contact angle measurements. Furthermore, the polymers could be dissolved in a range of polar organic solvents such as dimethylformamide, propylene carbonate, and dimethyl sulfoxide making these polymers interesting candidates for wet processing methods.

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