1256262-62-0

Upstream product

• 6737-42-4 1,3-bis-(diphenylphosphino)propane 
• 55659-61-5 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) 
• 95-46-5 2-methylphenyl bromide 

Relevant academic research and scientific papers

Direct visualization of microphase separation in block copoly(3-alkylthiophene)s

A poly(3-octylthiophene)-block-poly(3-butylthiophene) block copolymer was synthesized in a one-pot block copolymerization reaction, starting from a functional o-tolyl initiator in order to maximize A-B diblock copolymer formation. First, the composition of this block copolymer is extensively studied using gel permeation chromatography (GPC) and 1H NMR measurements. A complete block copolymer formation is obtained with almost equal block length; B-A-B block copolymer contamination is shown to be very limited. In a second part, the self-assembly was analysed through differential scanning calorimetry (DSC), atomic force microscopy (AFM) and scanning tunnelling microscopy (STM) measurements, focusing on the microphase separation. A direct visualization of the different microphases can be obtained with STM.

π-complexation in nickel-catalyzed cross-coupling reactions

The kinetic isotope effect (KIE) is used to experimentally elucidate the first irreversible step in oxidative addition reactions of a zerovalent nickel catalyst to a set of haloarene substrates. Halogenated o-methylbenzene, dimethoxybenzene, and thiophene derivatives undergo intramolecular oxidative addition through irreversible π-complexation. Density functional theory computations at the B3LYP-D3/TZ2P-LANL2TZ(f)-LANL08d level predict η2-bound π-complexes are generally stable relative to a solvated catalyst plus free substrate and that ring-walking of the Ni(0) catalyst and intramolecular oxidative addition are facile in these intermediates.

Synthesis and postfunctionalization of rod-coil diblock and coil-rod-coil triblock copolymers composed of poly(3-hexylthiophene) and poly(4-(4′-N, N -dihexylaminophenylethynyl)styrene) segments

Poly(3-hexylthiophene) (P3HT) with a bromobutyl functional group at the ω-chain-end (P3HT-C4Br) and P3HT with bromobutyl functional groups at the α,ω-chain-ends (BrC4-P3HT-C4Br) were synthesized by selecting the appropriate initiators for the Grignard metathesis (GRIM) polymerization. The high end-functionality was confirmed by matrix assisted laser desorption-ionization time-of-flight (MALDI-TOF) mass spectrometry. These polymers were efficiently reacted with the living anionic polymers of 4-(4′-N,N-dihexylaminophenylethynyl)styrene (DHPS) to yield novel rod-coil diblock and coil-rod-coil triblock copolymers composed of rigid P3HT and flexible poly(4-(4′-N,N-dihexylaminophenylethynyl)styrene) (PDHPS) segments. The expected structures of the block copolymers were confirmed by size exclusion chromatography (SEC), proton nuclear magnetic resonance (1H NMR), and Fourier transform infrared (FT-IR) spectroscopies. Furthermore, the side chain alkynes of the PDHPS segments of both P3HT-b-PDHPS and PDHPS-b-P3HT-b-PDHPS were quantitatively functionalized by a [2 + 2] cycloaddition followed by a cycloreversion with tetracyanoethylene (TCNE), producing the corresponding block copolymers with donor-acceptor moieties in the flexible polystyrene segments. The formation of the new chromophores was confirmed by UV-vis spectroscopy and cyclic voltammetry (CV), which revealed strong intramolecular charge-transfer bands and redox activities ascribed to the formed donor-acceptor moieties. The thermal properties and surface morphology of the block copolymers were also evaluated by differential scanning calorimetry (DSC), atomic force microscopy (AFM) observations, and small-angle and wide-angle X-ray scattering (SAXS and WAXS). This is the first report about the development of P3HT-based block copolymers with tunable optoelectronic properties, which was achieved by the combined synthetic techniques of the GRIM polymerization, living anionic polymerization, and click postfunctionalization.