Stille Polycondensation for Synthesis of Functional Materials

Department of Chemistry and the James Franck Institute, the University of Chicago, 929 E. 57th Street, Chicago, Illinois 60637, USA.
Chemical Reviews (Impact Factor: 46.57). 02/2011; 111(3):1493-528. DOI: 10.1021/cr100320w
Source: PubMed


The progress made in the development of the Stille coupling reaction for the preparation of functional polymers has been tremendous is presented. Corey and co-workers reported acceleration of the Stille reactions involving sterically hindered vinyl stannanes using CuCl as an additive. Fu and co-workers reported a general method for couplings involving chlorides and Chan et al. reported the use of Stille coupling to prepare rhenium-containing polymers for organic solar cell applications. McCulloch and co-workers prepared a thieno[2,3-b]-thiophene based polymer, where thieno- [2,3-b]thiophene was incorporated into a polythiophene backbone using the Stille polycondensation. In 2010, Yu et al. synthesized copolymer of benzo[1,2-b:4,5-b']dithiophene and thieno[3,4-b]thiophene using Pd(PPh3)4 as catalyst. Ng et al. prepared a series of thiophene-based polymers using Pd(PPh3) 2Cl2 as catalyst, though the molecular weights were relatively low.

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    • "Such impurities can increase trap-assisted recombination processes in polymer-fullerene BHJ solar cells, and can have detrimental effects on device efficiency and lifetime [4e6] at concentrations as low as 0.01 wt% (100 ppm) [7]. The conjugated polymers used in OPVs are generally synthesised through Stille [8] [9] or Suzuki [10] coupling reactions that are catalysed by palladium (Pd) complexes . These complexes degrade during the polymerisation, creating palladium nanoparticles that bind to the polymer and are difficult to remove [5] [11] [12]. "
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    ABSTRACT: Palladium (Pd) is commonly used as a catalyst in the polymerisation of conjugated polymers such as poly [N-9 0-heptadecanyl-2,7-carbozole-alt-5,5-(4 0 ,7 0-di-2-thenyl-2 0 ,1 0 ,3 0-benzothiadiazole)] (PCDTBT). Here we explore the effect of residual catalyst on the performance of organic photovoltaic devices (OPVs) based on a PCDTBT:fullerene thin-film blend. We find that as the relative concentration of Pd increases, the power conversion efficiency of the PV is reduced, dropping from 4.55% to 2.42% as the Pd concentration was increased to 2570 ppm (relative to that of the PCDTBT). This reduction in efficiency resulted primarily from a reduction in PV fill factor and shunt-resistance, indicating the presence of current-shunts within the device. Using optical microscopy, laser beam induced current mapping and scanning electron microscopy, we are able to demonstrate that such current shunts are associated with micron-sized aggregates of Pd-containing nanoparticles. We show that the presence of high concentrations of Pd within a PCDTBT OPV contribute to a larger drop in efficiency during the initial 'burn-in' period.
    Full-text · Article · Dec 2015 · Organic Electronics
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    • "Overall, to tune the electron-pushing or/ and electron-withdrawing effects of the functional groups has become an important method in molecular design of polymer photovoltaic materials. From the aspect of organic synthesis, most of conjugated polymers with the DeA structure were synthesized by the palladium catalyzed polycondensation reactions, especially by the Suzuki [39] or Stille [40] [41] coupling reactions. Since the Suzuki and Stille polycondensation reactions are adapted to the monomers with varied functional groups, the conjugated polymers substituted by alkoxyl, alkyl, alkylsulfonyl, carboxyl, acylamino and so on can be easily prepared. "
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    ABSTRACT: Molecular designing of photovoltaic polymers based on benzodithiophene (BDT) building blocks for high power conversion efficiency (PCE) in polymer solar cells (PSCs) arouse much attention in the past few years. To meliorate the energy levels of photovoltaic polymers featuring alkylthio substituted BDT units, a novel post-polymerization oxidation method was proposed applied in converting sulfur atom into sulfonyl group on side chains of the pristine polymer PBT-S. After treating with tiny amount of meta-chloroperoxybenzoic acid (m-CPBA) and hydrogen peroxide (H2O2), two batches of the target polymers, namely, PBT-SO2-M and PBT-SO2-H were prepared for the first time, respectively. The photochemical and electrochemical results indicate that both the HOMO levels are distinctly dropped with almost no influence on band gaps by introducing strong electron-withdrawing sulfonyl groups on side chains of BDT. Accordingly, the photovoltaic results reveal that the Voc of devices based on PBT-SO2-M and PBT-SO2-H are 0.81, 0.71 V which are 0.17 and 0.07 V higher than that of pristine polymer PBT-S, respectively. Moreover, the Jsc and PCE of PBT-SO2-H devices are comparable with those of the devices based on PBT-S. Overall, this work suggests that the molecular energy levels of D-A copolymers can be effectively tuned by a post-oxidation method.
    Full-text · Article · Oct 2015 · Organic Electronics
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    ABSTRACT: Acetylene-bridged N-confused porphyrin (NCP) dimers were synthesized by Stille coupling reactions. Moderate electronic interaction between the NCP chromophores was observed in the inner-3H tautomers while strong interaction was observed in the inner-2H tautomers.
    No preview · Article · Sep 2011 · Chemistry Letters
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