Direct Heteroarylation Guidelines for Well-Defined Thiophene-Based Conjugated Molecules.

Direct (hetero)arylation polymerization (DHAP) shows great promise for simple, low cost, and benign preparation of conjugated polymers. However, coupling selectivity has always posed a problem. Herein, direct (hetero)arylation was studied on small molecule models to develop suitable conditions for C-C couplings between 2-methylthiophene acting as an electron-donating moiety and 2-thiophenecarbonitrile acting as an electron-withdrawing moiety, when one of the partners is brominated. We observed that the best conditions are obtained when the electron-withdrawing moiety is halogenated.

Biosourced Vanillin-Based Building Blocks for Organic Electronic Materials.

Forest biomass is viewed as a significant source of organic carbon and thus the ideal replacement of petroleum products. From the resources derived from biomass, lignocellulose is the most abundant biobased material on earth. One of the aromatic added value compounds obtained from the depolymerization of lignin is vanillin. Here, we report the preparation of new compounds having benzothiophene, indole, isatin, benzofuroxan, benzofurazan, benzothiadiazole, and phthalimide heteroaromatic ring structures. More precisely, our results show that vanillin can be used as a biosourced starting material for the preparation of a variety of aromatic dibrominated monomers. X-ray crystallography on single crystals was also performed to obtain meaningful information on their solid-state ordering. This work opens the way to new, sustainable, biosourced aromatic materials (small molecules or polymers) for organic electronics.

Air-Processed, Stable Organic Solar Cells with High Power Conversion Efficiency of 7.41.

High efficiency, excellent stability, and air processability are all important factors to consider in endeavoring to push forward the real-world application of organic solar cells. Herein, an air-processed inverted photovoltaic device built upon a low-bandgap, air-stable, phenanthridinone-based ter-polymer (C150 H218 N6 O6 S4 )n (PDPPPTD) and [6,6]-phenyl-C61 -butyric acid methyl ester (PC61 BM) without involving any additive engineering processes yields a high efficiency of 6.34%. The PDPPPTD/PC61 BM devices also exhibit superior thermal stability and photo-stability as well as long-term stability in ambient atmosphere without any device encapsulation, which show less performance decay as compared to most of the reported organic solar cells. In view of their great potential, solvent additive engineering via adding p-anisaldehyde (AA) is attempted, leading to a further improved efficiency of 7.41%, one of the highest efficiencies for all air-processed and stable organic photovoltaic devices. Moreover, the device stability under different ambient conditions is also further improved with the AA additive engineering. Various characterizations are conducted to probe the structural, morphology, and chemical information in order to correlate the structure with photovoltaic performance. This work paves a way for developing a new generation of air-processable organic solar cells for possible commercial application.

CH Activation as a Shortcut to Conjugated Polymer Synthesis.

Direct (hetero)arylation polymerization exploits the palladium-catalyzed activation of aromatic CH bonds for the atom-economical synthesis of conjugated polymers for a wide range of applications. This account outlines how direct arylation methodologies overcome many of the limitations of contemporary polymerization techniques at both the research and production scale, and explains how monomer design and reaction conditions must be tailored to ensure high polymer molecular weight, yield, and structural integrity. Current research aims to improve further this reaction's profile as a sustainable methodology while at the same time making it competitive with the Migita-Stille and Miyaura-Suzuki polymerizations both in scope of accessible structures and synthetic efficiency. This feature article charts the recent developments and future directions of CH activation research as it moves toward becoming at once an industrially feasible, environmentally friendly, and synthetically powerful polymerization technique.

Direct (Hetero)arylation Polymerization: Simplicity for Conjugated Polymer Synthesis.

Direct (hetero)arylation polymerization (DHAP) has recently been established as an environmentally benign method for the preparation of conjugated polymers. This synthetic tool features the formation of C-C bonds between halogenated (hetero)arenes and simple (hetero)arenes with active C-H bonds, thereby circumventing the preparation of organometallic derivatives and decreasing the overall production cost of conjugated polymers. Since its inception, selectivity and reactivity of DHAP procedures have been improved tremendously through the careful scrutinity of polymerization outcomes and the fine-tuning of reaction conditions. A broad range of monomers, from simple arenes to complex functionalized heteroarenes, can now be readily polymerized. The successful application of DHAP now leads to nearly defect-free conjugated polymers possessing comparable, if not slightly better, characteristics than their counterparts prepared using classical cross-coupling methods. This comprehensive review describes the mechanisms involved in this process from experimental and theoretical standpoints, presents an up-to-date compendium of materials obtained by this means, and exposes its current limitations and challenges.

Theoretical Calculations for Highly Selective Direct Heteroarylation Polymerization: New Nitrile-Substituted Dithienyl-Diketopyrrolopyrrole-Based Polymers.

Direct Heteroarylation Polymerization (DHAP) is becoming a valuable alternative to classical polymerization methods being used to synthesize π-conjugated polymers for organic electronics applications. In previous work, we showed that theoretical calculations on activation energy (Ea) of the C⁻H bonds were helpful to rationalize and predict the selectivity of the DHAP. For readers' convenience, we have gathered in this work all our previous theoretical calculations on Ea and performed new ones. Those theoretical calculations cover now most of the widely utilized electron-rich and electron-poor moieties studied in organic electronics like dithienyl-diketopyrrolopyrrole (DT-DPP) derivatives. Theoretical calculations reported herein show strong modulation of the Ea of C⁻H bond on DT-DPP when a bromine atom or strong electron withdrawing groups (such as fluorine or nitrile) are added to the thienyl moiety. Based on those theoretical calculations, new cyanated dithienyl-diketopyrrolopyrrole (CNDT-DPP) monomers and copolymers were prepared by DHAP and their electro-optical properties were compared with their non-fluorinated and fluorinated analogues.

Robust Direct (Hetero)arylation Polymerization in Biphasic Conditions.

The synthesis of conjugated polymers from direct (hetero)arylation polymerization (DHAP) has been achieved for the first time using biphasic water/toluene conditions. This protocol is robust enough to form polymers even when air is introduced in the system. General reactivity is demonstrated for a single set of polymerization conditions with thienyl- or phenyl-based substrates, whether they are electron-rich or electron-poor. Complete characterization from differential scanning calorimetry and 1H NMR and UV-vis-NIR spectroscopies is presented, demonstrating this DHAP protocol offers comparable or better properties than the very best values published thus far. High molecular weights are obtained, showcasing the perfect equilibrium of reactivity and selectivity attained with this method. Moreover, this efficient and versatile methodology, which also uses low-cost, "wet" reagents, is scalable and done at ambient pressure.

Salt-induced thermochromism of a conjugated polyelectrolyte.

We report here the photophysical properties of a water-soluble conjugated polythiophene with cationic side-chains. When dissolved in aqueous buffer solution (PBS, phosphate buffered saline), there is ordering of the polymer chains due to the presence of the salts, in contrast to pure water, where a random-coil conformation is adopted at room temperature. The ordering leads to a pronounced colour change of the solution (the absorption maximum shifts from 400 nm to 525 nm). Combining resonance Raman spectroscopy with density functional theory computations, we show a significant backbone planarization in the ordered phase. Moreover, the ratio of ordered phase to random-coil phase in PBS solution, as well as the extent of intermolecular interactions in the ordered phase, can be tuned by varying the temperature. Femtosecond transient absorption spectroscopy reveals that the excited-state behaviour of the polyelectrolyte is strongly affected by the degree of ordering. While triplet state formation is favoured in the random-coil chains, the ordered chains show a weak yield of polarons, related to interchain interactions. The investigated polyelectrolyte has been previously used as a biological DNA sensor, based on optical transduction when the conformation of the polyelectrolyte changes during assembly with the biomolecule. Therefore, our results, by correlating the photophysical properties of the polyelectrolyte to backbone and intermolecular conformation in a biologically relevant buffer, provide a significant step forward in understanding the mechanism of the biological sensing.

Direct (Hetero)arylation Polymerization: Trends and Perspectives.

Conjugated polymers have attracted much attention in recent years, as they can combine the best features of metals or inorganic semiconducting materials (excellent electrical and optical properties) with those of synthetic polymers (mechanical flexibility, simple processing, and low-cost production), thereby creating altogether new scientific synergies and technological opportunities. In the search for more efficient synthetic methods for the preparation of conjugated polymers, this Perspective reports advances in the field of direct (hetero)arylation polymerization. This recently developed polymerization method encompasses the formation of carbon-carbon bonds between simple (hetero)arenes and (hetero)aryl halides, reducing both the number of synthetic steps and the production of organometallic byproducts. Along these lines, we describe the most general and adaptable reaction conditions for the preparation of high-molecular-weight, defect-free conjugated polymers. We also discuss the bottleneck presented by the utilization of certain brominated thiophene units and propose some potential solutions. It is, however, firmly believed that this polymerization method will become a versatile tool in the field of conjugated polymers by providing a desirable atom-economical alternative to standard cross-coupling polymerization reactions.

Qualitative analysis of bulk-heterojunction solar cells without device fabrication: an elegant and contactless method.

The enormous synthetic efforts on novel solar cell materials require a reliable and fast technique for the rapid screening of novel donor/acceptor combinations in order to quickly and reliably estimate their optimized parameters. Here, we report the applicability of such a versatile and fast evaluation technique for bulk heterojunction (BHJ) organic photovoltaics (OPV) by utilizing a steady-state photoluminescence (PL) method confirmed by electroluminescence (EL) measurements. A strong relation has been observed between the residual singlet emission and the charge transfer state emission in the blend. Using this relation, a figure of merit (FOM) is defined from photoluminescence and also electroluminescence measurements for qualitative analysis and shown to precisely anticipate the optimized blend parameters of bulk heterojunction films. Photoluminescence allows contactless evaluation of the photoactive layer and can be used to predict the optimized conditions for the best polymer-fullerene combination. Most interestingly, the contactless, PL-based FOM method has the potential to be integrated as a fast and reliable inline tool for quality control and material optimization.

Direct (hetero)arylation: a new tool for polymer chemists.

The coupling of aryl halides with catalytically activated aryl C-H bonds provides a desirable and atom-economical alternative to standard cross-coupling reactions for the construction of new C-C bonds. The reaction, termed direct (hetero)arylation, is believed to follow a base-assisted, concerted metalation-deprotonation (CMD) pathway. During this process, carboxylate or carbonate anions coordinate to the metal center, typically palladium, in situ and assist in the deprotonation transition state. Researchers have employed this methodology with numerous arenes and heteroarenes, including substituted benzenes, perfluorinated benzenes, and thiophenes. Thiophene substrates have demonstrated high reactivity toward C-H bond activation when appropriately substituted with electron-rich and/or electron-deficient groups. Because of the pervasive use of thiophenes in materials for organic electronics, researchers have used this chemistry to modularly prepare conjugated small molecules and, more recently, conjugated polymers. Although optimization of reaction conditions such as solvent system, phosphine ligand, carboxylate additives, temperature, and time is necessary for efficient C-H bond reactivity of each monomer, direct (hetero)arylation polymerization (DHAP) can afford high yielding polymeric materials with elevated molecular weights. The properties of these materials often rival those of polymers prepared by traditional methods. Moreover, DHAP provides a facile means for the synthesis of polymers that were previously inaccessible or difficult to prepare due to the instability of organometallic monomers. The major downfall of direct (hetero)arylation, however, is the lack of C-H bond selectivity, particularly for thiophene substrates, which can result in cross-linked material during polymerization reactions. Further fine-tuning of reaction conditions such as temperature and reaction time may suppress these unwanted side reactions. Alternatively, new monomers can be designed where other reactive bonds are blocked, either sterically or by substitution with unreactive alkyl or halogen groups. In this Account, we illustrate these methods and present examples of DHAP reactions that involve the preparation of common homopolymers used in organic electronics (P3HT, PEDOT, PProDOT), copolymers formed by activation of electron-rich (bithiophene, fused bithiophenes) and electron-deficient monomers (TPD, 1,2,4,5-tetrafluorobenzene, 2,2'-bithiazole). Our group is optimizing these reactions and developing ways to make DHAP a common atom-economical synthetic tool for polymer chemists.

Highly Transmissive, Processable, Highly Conducting and Stable Polythiophene Derivatives via Direct (Hetero)arylation Polymerization.

The development of modern optoelectronic devices increases the need for lightweight and flexible transparent conductors. It is thus essential to develop new eco-friendly materials that can be easily processed for the fabrication of such devices. For this purpose, the synthesis of self-doped, highly conducting, transmissive, and water-processable polythiophene derivatives was performed via the direct heteroarylation polymerization method and a protection/deprotection strategy. Stable conductivities up to 1000 S cm-1 have been obtained. Champion materials (P1 and P7) were scaled and processed via the roll-to-roll compatible slot-die coating method to demonstrate their large area applicability. The best coated films exhibited optical transmittance greater than 79% at 550 nm with sheet resistances of 116 Ω â–¡-1. These values are comparable to indium-tin oxide on plastic and thus present a viable alternative to metal oxide-based electrodes.

Highly-efficient charge separation and polaron delocalization in polymer-fullerene bulk-heterojunctions: a comparative multi-frequency EPR and DFT study.

The ongoing depletion of fossil fuels has led to an intensive search for additional renewable energy sources. Solar-based technologies could provide sufficient energy to satisfy the global economic demands in the near future. Photovoltaic (PV) cells are the most promising man-made devices for direct solar energy utilization. Understanding the charge separation and charge transport in PV materials at a molecular level is crucial for improving the efficiency of the solar cells. Here, we use light-induced EPR spectroscopy combined with DFT calculations to study the electronic structure of charge separated states in blends of polymers (P3HT, PCDTBT, and PTB7) and fullerene derivatives (C60-PCBM and C70-PCBM). Solar cells made with the same composites as active layers show power conversion efficiencies of 3.3% (P3HT), 6.1% (PCDTBT), and 7.3% (PTB7), respectively. Upon illumination of these composites, two paramagnetic species are formed due to photo-induced electron transfer between the conjugated polymer and the fullerene. They are the positive, P(+), and negative, P(-), polarons on the polymer backbone and fullerene cage, respectively, and correspond to radical cations and radical anions. Using the high spectral resolution of high-frequency EPR (130 GHz), the EPR spectra of these species were resolved and principal components of the g-tensors were assigned. Light-induced pulsed ENDOR spectroscopy allowed the determination of (1)H hyperfine coupling constants of photogenerated positive and negative polarons. The experimental results obtained for the different polymer-fullerene composites have been compared with DFT calculations, revealing that in all three systems the positive polaron is distributed over distances of 40-60 Å on the polymer chain. This corresponds to about 15 thiophene units for P3HT, approximately three units for PCDTBT, and about three to four units for PTB7. No spin density delocalization between neighboring fullerene molecules was detected by EPR. Strong delocalization of the positive polaron on the polymer donor is an important reason for the efficient charge separation in bulk heterojunction systems as it minimizes the wasteful process of charge recombination. The combination of advanced EPR spectroscopy and DFT is a powerful approach for investigation of light-induced charge dynamics in organic photovoltaic materials.

Bithiopheneimide-dithienosilole/dithienogermole copolymers for efficient solar cells: information from structure-property-device performance correlations and comparison to thieno[3,4-c]pyrrole-4,6-dione analogues.

Rational creation of polymeric semiconductors from novel building blocks is critical to polymer solar cell (PSC) development. We report a new series of bithiopheneimide-based donor-acceptor copolymers for bulk-heterojunction (BHJ) PSCs. The bithiopheneimide electron-deficiency compresses polymer bandgaps and lowers the HOMOs--essential to maximize power conversion efficiency (PCE). While the dithiophene bridge progression R(2)Si→R(2)Ge minimally impacts bandgaps, it substantially alters the HOMO energies. Furthermore, imide N-substituent variation has negligible impact on polymer opto-electrical properties, but greatly affects solubility and microstructure. Grazing incidence wide-angle X-ray scattering (GIWAXS) indicates that branched N-alkyl substituents increased polymer π-π spacings vs linear N-alkyl substituents, and the dithienosilole-based PBTISi series exhibits more ordered packing than the dithienogermole-based PBTIGe analogues. Further insights into structure-property-device performance correlations are provided by a thieno[3,4-c]pyrrole-4,6-dione (TPD)-dithienosilole copolymer PTPDSi. DFT computation and optical spectroscopy show that the TPD-based polymers achieve greater subunit-subunit coplanarity via intramolecular (thienyl)S···O(carbonyl) interactions, and GIWAXS indicates that PBTISi-C8 has lower lamellar ordering, but closer π-π spacing than does the TPD-based analogue. Inverted BHJ solar cells using bithiopheneimide-based polymer as donor and PC(71)BM as acceptor exhibit promising device performance with PCEs up to 6.41% and V(oc) > 0.80 V. In analogous cells, the TPD analogue exhibits 0.08 V higher V(oc) with an enhanced PCE of 6.83%, mainly attributable to the lower-lying HOMO induced by the higher imide group density. These results demonstrate the potential of BTI-based polymers for high-performance solar cells, and provide generalizable insights into structure-property relationships in TPD, BTI, and related polymer semiconductors.

Low-cost synthesis and physical characterization of thieno[3,4-c]pyrrole-4,6-dione-based polymers.

The improved synthesis of thieno[3,4-c]pyrrole-4,6-dione (TPD) monomers, including Gewald thiophene ring formation, a Sandmeyer-type reaction, and neat condensation with an amine, is presented. This protocol enables faster, cheaper, and more efficient preparation of TPD units in comparison to traditional methods. Furthermore, a series of TPD homo- and pseudohomopolymers bearing various alkyl chains was synthesized via a direct heteroarylation polymerization (DHAP) procedure. UV-visible absorption and powder X-ray diffraction measurements revealed the relationship between the ratio of branched to linear alkyl chains and the optoelectronic properties of the polymers as well as their packing in the solid state.

Bulk heterojunction solar cells using thieno[3,4-c]pyrrole-4,6-dione and dithieno[3,2-b:2',3'-d]silole copolymer with a power conversion efficiency of 7.3%.

A new alternating copolymer of dithienosilole and thienopyrrole-4,6-dione (PDTSTPD) possesses both a low optical bandgap (1.73 eV) and a deep highest occupied molecular orbital energy level (5.57 eV). The introduction of branched alkyl chains to the dithienosilole unit was found to be critical for the improvement of the polymer solubility. When blended with PC(71)BM, PDTSTPD exhibited a power conversion efficiency of 7.3% on the photovoltaic devices with an active area of 1 cm(2).

Amplification strategy using aggregates of ferrocene-containing cationic polythiophene for sensitive and specific electrochemical detection of DNA.

We report a new electrochemical amplification strategy for an ultrasensitive electrochemical detection of DNA sequences using aggregates composed of a water-soluble, ferrocene-functionalized polythiophene. A two-step hybridization is performed at one addressing surface with PNA capture probes whereas the electrochemical detection is done on an electrode nearby. Specific and quantitative detection of DNA targets with a detection limit of 4 × 10(-16) M (about 4 zeptomoles or about 2500 copies of oligonucleotides) was achieved.

Exciton formation, relaxation, and decay in PCDTBT.

The nature and time evolution of the primary excitations in the pristine conjugated polymer, PCDTBT, are investigated by femtosecond-resolved fluorescence up-conversion spectroscopy. The extensive study includes data from PCDTBT thin film and from PCDTBT in chlorobenzene solution, compares the fluorescence dynamics for several excitation and emission wavelengths, and is complemented by polarization-sensitive measurements. The results are consistent with the photogeneration of mobile electrons and holes by interband π-π* transitions, which then self-localize within about 100 fs and evolve to a bound singlet exciton state in less than 1 ps. The excitons subsequently undergo successive migrations to lower energy localized states, which exist as a result of disorder. In parallel, there is also slow conformational relaxation of the polymer backbone. While the initial self-localization occurs faster than the time resolution of our experiment, the exciton formation, exciton migration, and conformational changes lead to a progressive relaxation of the inhomogeneously broadened emission spectrum with time constants ranging from about 500 fs to tens of picoseconds. The time scales found here for the relaxation processes in pristine PCDTBT are compared to the time scale (<0.2 ps) previously reported for photoinduced charge transfer in phase-separated PCDTBT:fullerene blends (Phys. Rev. B 2010, 81, 125210). We point out that exciton formation and migration in PCDTBT occur at times much longer than the ultrafast photoinduced electron transfer time in PCDTBT:fullerene blends. This disparity in time scales is not consistent with the commonly proposed idea that photoinduced charge separation occurs after diffusion of the polymer exciton to a fullerene interface. We therefore discuss alternative mechanisms that are consistent with ultrafast charge separation before localization of the primary excitation to form a bound exciton.