AB- Versus AA+BB-Suzuki Polycondensation: A Palladium/Tris(tert-butyl)phosphine Catalyst Can Outperform Conventional Catalysts.

A Pd/Pt-Bu3 catalyst having bulky, electron-rich ligands significantly outperforms conventional "step-growth catalysts" Pd(PPh3 )4 and Pd(Po-Tol3 )3 in the Suzuki polycondensation of the AB-type arylene-based monomers, such as some of the substituted fluorenes, carbazoles, and phenylenes. In the AA+BB polycondensation, Pd/Pt-Bu3 also performs better under homogeneous reaction conditions, in combination with the organic base Et4 NOH. The superior performance of Pd/Pt-Bu3 is discussed in terms of its higher reactivity in the oxidative addition step and inherent advantages of the intramolecular catalyst transfer, which is a key step joining catalytic cycles of the AB-polycondensation. These findings are applied to the synthesis of a carbazole-based copolymer designed for the use as a hole conductor in solution-processed organic light-emitting diodes.

Laser Treatment as Sintering Process for Dispenser Printed Bismuth Telluride Based Paste.

Laser sintering as a thermal post treatment method for dispenser printed p- and n-type bismuth telluride based thermoelectric paste materials was investigated. A high-power fiber laser (600 W, 1064 nm) was used in combination with a scanning system to achieve high processing speed. A Design of Experiment (DoE) approach was used to identify the most relevant processing parameters. Printed layers were laser treated with different process parameters and the achieved sheet resistance, electrical conductivity, and Seebeck coefficient are compared to tube furnace processed reference specimen. For p-type material, electrical conductivity of 22 S/cm was achieved, compared to 15 S/cm in tube furnace process. For n-type material, conductivity achieved by laser process was much lower (7 S/cm) compared to 88 S/cm in furnace process. Also, Seebeck coefficient decreases during laser processing (40-70 µV/K and -110 µV/K) compared to the oven process (251 µV/K and -142 µV/K) for p- and n-type material. DoE did not yet deliver a set of optimum processing parameters, but supports doubts about the applicability of area specific laser energy density as a single parameter to optimize laser sintering process.

Influence of Semiconductor Thickness and Molecular Weight on the Charge Transport of a Naphthalenediimide-Based Copolymer in Thin-Film Transistors.

The N-type semiconducting polymer, P(NDI2OD-T2), with different molecular weights (MW=23, 72, and 250 kg/mol) was used for the fabrication of field-effect transistors (FETs) with different semiconductor layer thicknesses. FETs with semiconductor layer thicknesses from ∼15 to 50 nm exhibit similar electron mobilities (µ's) of 0.2-0.45 cm2 V(-1) s(-1). Reduction of the active film thickness led to decreased µ values; however, FETs with ∼2 and ∼5 nm thick P(NDI2OD-T2) films still exhibit substantial µ's of 0.01-0.02 and ∼10(-4) cm2 V(-1) s(-1), respectively. Interestingly, the lowest molecular weight sample (P-23, MW≈23 kg/mol, polydispersity index (PDI)=1.9) exhibited higher µ than the highest molecular weight sample (P-250, MW≈250 kg/mol, PDI=2.3) measured for thicker devices (15-50 nm). This is rather unusual behavior because typically charge carrier mobility increases with MW where improved grain-to-grain connectivity usually enhances transport events. We attribute this result to the high crystallinity of the lowest MW sample, as confirmed by differential scanning calorimetry and X-ray diffraction studies, which may (over)compensate for other effects.

Palladium-catalyzed chain-growth polycondensation of AB-type monomers: high catalyst turnover and polymerization rates.

Chain-growth catalyst-transfer polycondensations of AB-type monomers is a new and rapidly developing tool for the preparation of well-defined π-conjugated (semiconducting) polymers for various optoelectronic applications. Herein, we report the Pd/PtBu3-catalyzed Negishi chain-growth polycondensation of AB-type monomers, which proceeds with unprecedented TONs of above 100,000 and TOFs of up to 280 s(-1). In contrast, related AA/BB-type step-growth polycondensation proceeds with two orders of magnitude lower TONs and TOFs. A similar trend was observed in Suzuki-type polycondensation. The key impact of the intramolecular (vs. intermolecular) catalyst-transfer process on both polymerization kinetics and catalyst lifetime has been revealed.

On the role of single regiodefects and polydispersity in regioregular poly(3-hexylthiophene): defect distribution, synthesis of defect-free chains, and a simple model for the determination of crystallinity.

Identifying structure formation in semicrystalline conjugated polymers is the fundamental basis to understand electronic processes in these materials. Although correlations between physical properties, structure formation, and device parameters of regioregular, semicrystalline poly(3-hexylthiophene) (P3HT) have been established, it has remained difficult to disentangle the influence of regioregularity, polydispersity, and molecular weight. Here we show that the most commonly used synthetic protocol for the synthesis of P3HT, the living Kumada catalyst transfer polycondensation (KCTP) with Ni(dppp)Cl(2) as the catalyst, leads to regioregular chains with one single tail-to-tail (TT) defect distributed over the whole chain, in contrast to the hitherto assumed exclusive location at the chain end. NMR end-group analysis and simulations are used to quantify this effect. A series of entirely defect-free P3HT materials with different molecular weights is synthesized via new, soluble nickel initiators. Data on structure formation in defect-free P3HT, as elucidated by various calorimetric and scattering experiments, allow the development of a simple model for estimating the degree of crystallinity. We find very good agreement for predicted and experimentally determined degrees of crystallinities as high as ∼70%. For Ni(dppp)Cl(2)-initiated chains comprising one distributed TT unit, the comparison of simulated crystallinities with calorimetric and optical measurements strongly suggests incorporation of the TT unit into the crystal lattice, which is accompanied by an increase in backbone torsion. Polydispersity is identified as a major parameter determining crystallinity within the molecular weight range investigated. We believe that the presented approach and results not only contribute to understanding structure formation in P3HT but are generally applicable to other semicrystalline conjugated polymers as well.

Chain-growth polymerization of unusual anion-radical monomers based on naphthalene diimide: a new route to well-defined n-type conjugated copolymers.

Strongly electron-deficient (n-type) main-chain π-conjugated polymers are commonly prepared via well-established step-growth polycondensation protocols which enable limited control over polymerization. Here we demonstrate that activated Zn and electron-deficient brominated thiophene-naphthalene diimide oligomers form anion-radical complexes instead of conventional Zn-organic derivatives. These highly unusual zinc complexes undergo Ni-catalyzed chain-growth polymerization leading to n-type conjugated polymers with controlled molecular weight, relatively narrow polydispersities, and specific end-functions.

Random catalyst walking along polymerized poly(3-hexylthiophene) chains in Kumada catalyst-transfer polycondensation.

A "walking" process of Ni catalysts during Kumada catalyst-transfer polycondensation along polymerizing poly(3-hexylthiophene), P3HT, chains was investigated. To simplify polymer end group identifications, a compound Br-C(6)H(4)-Ni(dppe)-Br was prepared and used as an externally addable initiator. Normally, aryl moieties present in initiators incorporate into the structure of the resulting P3HT as the starting groups. We demonstrate that due to the presence of the C-Br group located in the para-position to the Ni substituent of the initiator, two different polymeric products are formed. One of them is the "normal" product, that is, P3HT with a para-bromophenyl end group, whereas another one has the phenyl ring inside the P3HT chain. The content of the product with the internal phenyl ring increases with the increase of the polymerization degree. Control experiments demonstrated that no intermolecular catalyst transfer takes place in the conditions used. Such results suggest that catalytic Ni(0) species are able to walk along the polymerizing chain containing many tens of thienyl rings up to the opposite end and can initiate polymerization there. Numerical analysis of a random hopping model was undertaken, which revealed that a combination of a random catalyst walking along the chain and a "sticking effect" at the end groups is operative in Kumada catalyst-transfer polycondensation.

Surface-initiated Kumada catalyst-transfer polycondensation of poly(9,9-dioctylfluorene) from organosilica particles: chain-confinement promoted beta-phase formation.

Surface-initiated Kumada catalyst-transfer polycondensation of poly(9,9-dioctylfluorene) (PFO) was performed from organosilica microparticles that resulted in PFO brushes with densely grafted PFO chains with a significantly enhanced propensity to adopt planar and ordered conformations (beta-phase).

Microparticle-supported conjugated polyelectrolyte brushes prepared by surface-initiated kumada catalyst transfer polycondensation for sensor applications.

A 'grafting-from' approach to synthesize microparticle-supported conjugated polyelectrolyte brushes is presented. Poly(3-bromohexylthiophene) is selectively grown from monodisperse organosilica microparticles by surface-initiated Kumada catalyst-transfer polycondensation (SI-KCTP) and then ionizable amino groups are introduced by a two-step polymer analogous transformation. Optical properties of the resulting microparticle-supported conjugated polyelectrolyte brushes were found to be dependent on the surrounding chemical environment and thus the particles are promising materials for sensor applications.

"Hairy" poly(3-hexylthiophene) particles prepared via surface-initiated Kumada catalyst-transfer polycondensation.

Herein, we present a new paradigm in the engineering of nanostructured hybrids between conjugated polymer and inorganic materials via a chain-growth surface-initiated Kumada catalyst-transfer polycondensation (SI-KCTP) from particles. Poly(3-hexylthiophene), P3HT, a benchmark material for organic electronics, was selectively grown by SI-KCTP from (nano)particles bearing surface-immobilized Ni catalysts supported by bidentate phosphorus ligands, that resulted in hairy (nano)particles with end-tethered P3HT chains. Densely grafted P3HT chains exhibit strongly altered optical properties compared to the untethered counterparts (red shift and vibronic fine structure in absorption and fluorescence spectra), as a result of efficient planarization and chain-aggregation. These effects are observed in solvents that are normally recognized as good solvents for P3HT (e.g., tetrahydrofurane). We attribute this to strong interchain interactions within densely grafted P3HT chains, which can be tuned by changing the surface curvature (or size) of the supporting particle. The hairy P3HT nanoparticles were successfully applied in bulk heterojunction solar cells.