Conventional semiconducting polymer synthesis typically involves transition metal-mediated coupling reactions that link aromatic units with single bonds along the backbone. Rotation around these bonds contributes to conformational and energetic disorder and therefore potentially limits charge delocalisation, whereas the use of transition metals presents difficulties for sustainability and application in biological environments. Here we show that a simple aldol condensation reaction can prepare polymers where double bonds lock-in a rigid backbone conformation, thus eliminating free rotation along the conjugated backbone. This polymerisation route requires neither organometallic monomers nor transition metal catalysts and offers a reliable design strategy to facilitate delocalisation of frontier molecular orbitals, elimination of energetic disorder arising from rotational torsion and allowing closer interchain electronic coupling. These characteristics are desirable for high charge carrier mobilities. Our polymers with a high electron affinity display long wavelength NIR absorption with air stable electron transport in solution processed organic thin film transistors.

Two azaisoindigo copolymers have been reported for high performance n-type and ambipolar thin film transistor application.

Precise control of the microstructure in organic semiconductors (OSCs) is essential for developing high‐performance organic electronic devices. Here, a comprehensive charge transport characterization of two recently reported rigid‐rod conjugated polymers that do not contain single bonds in the main chain is reported. It is demonstrated that the molecular design of the polymer makes it possible to achieve an extended linear backbone structure, which can be directly visualized by high‐resolution scanning tunneling microscopy (STM). The rigid structure of the polymers allows the formation of thin films with uniaxially aligned polymer chains by using a simple one‐step solution‐shear/bar coating technique. These aligned films show a high optical anisotropy with a dichroic ratio of up to a factor of 6. Transport measurements performed using top‐gate bottom‐contact field‐effect transistors exhibit a high saturation electron mobility of 0.2 cm2 V−1 s−1 along the alignment direction, which is more than six times higher than the value reported in the previous work. This work demonstrates that this new class of polymers is able to achieve mobility values comparable to state‐of‐the‐art n‐type polymers and identifies an effective processing strategy for this class of rigid‐rod polymer system to optimize their charge transport properties.

A novel fused heterocycle-flanked diketopyrrolopyrrole (DPP) monomer, thieno[2,3-b]pyridine diketopyrrolopyrrole (TPDPP), was designed and synthesized. When copolymerized with 3,4-difluorothiophene using Stille coupling polymerization, the new polymer pTPDPP-TF possesses a highly planar conjugated polymer backbone due to the fused thieno[2,3b]pyridine flanking unit that effectively alleviates the steric hindrance both with the central DPP core as well as the 3,4-difluorothiophene repeat unit. This new polymer exhibits a high electron affinity (EA) of-4.1 eV and was successfully utilized as an n-type polymer semiconductor for applications in organic field-effect transistors (OFETs) and all polymer solar cells. A promising ntype charge carrier mobility of 0.1 cm 2 V-1 s-1 was obtained in bottom-contact, top-gate OFETs and power conversion efficiency (PCE) of 2.72 % with a high open-circuit voltage (V OC) of 1.04 V was achieved for all polymer solar cells using PTB7-Th as the polymer donor. INTRODUCTION Solution-processable polymer semiconductors are promising candidates to realize next-generation lightweight and flexible electronics, such as organic field-effect transistors (OFETs) and organic solar cells (OSCs), via low cost and large area printing. The last decade has witnessed a tremendous advance in p-type polymer semiconductors with hole mobilities surpassing 10 cm 2 V-1 s-1 in OFETs 1,2 and power conversion efficiencies (PCEs) above 11% in OSCs. 3,4 To achieve broad applications of organic electronics such as organic complementary circuits and all polymer solar cells, congruent performances for both p-and n-type polymer semiconductors are desired. However, the progress in n-type polymer semiconductor development

We investigate the charge transport physics of a previously unidentified class of electron-deficient conjugated polymers that do not contain any single bonds linking monomer units along the backbone but only double-bond linkages. Such polymers would be expected to behave as rigid rods, but little is known about their actual chain conformations and electronic structure. Here, we present a detailed study of the structural and charge transport properties of a family of four such polymers. By adopting a copolymer design, we achieve high electron mobilities up to 0.5 cm2 V−1 s−1. Field-induced electron spin resonance measurements of charge dynamics provide evidence for relatively slow hopping over, however, long distances. Our work provides important insights into the factors that limit charge transport in this unique class of polymers and allows us to identify molecular design strategies for achieving even higher levels of performance.

The measurement of the mechanical properties of conjugated polymers can reveal highly relevant information linking optoelectronic properties to underlying microstructures and the knowledge of the glass transition temperature (Tg) is paramount for informing the choice of processing conditions and for interpreting the thermal stability of devices. In this work, we use dynamical mechanical analysis to determine the Tg of a range of state‐of‐the‐art conjugated polymers with different degrees of crystallinity that are widely studied for applications in organic field‐effect transistors. We compare our measured values for Tg to the theoretical value predicted by a recent work based on the concept of effective mobility ζ. The comparison shows that for conjugated polymers with a modest length of the monomer units, the Tg values agree well with theoretically predictions. However, for the near‐amorphous, indacenodithiophene–benzothiadiazole family of polymers with more extended backbone units, values for Tg appear to be significantly higher, predicted by theory. However, values for Tg are correlated with the sub‐bandgap optical absorption suggesting the possible role of the interchain short contacts within materials’ amorphous domains.

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A cascade reaction has been developed for the synthesis of lactonamycin. In this paper, we demonstrate that a transition-metal-free thermal ene-diyne cyclization can be used for the construction of the entire core of the antibiotic lactonamycin and anticancer agent lactonamycin Z.