Synthesis and Structure-Property Relationships in Regioisomeric Alternating Borane-Terthiophene Polymers.

Main-chain boron-containing π-conjugated polymers are attractive for organic electronic, sensing, and imaging applications. Alternating terthiophene-borane polymers were prepared and the effects of regioisomeric attachment of the conjugated linker and variations in the electronic effect of the pendent aryl groups (2,4,6-tri-tert-butylphenyl, Mes*; 2,4,6-tris(trifluoromethyl)phenyl, FMes) examined. Pd2 dba3 /P(t-Bu)3 -catalyzed Stille polymerization of arylbis(2-thienyl)borane and arylbis(3-thienylborane) with 2,5-bis(trimethylstannyl)thiophene at 120 °C gave polymers with appreciable molecular weight but MALDI-TOF MS analyses showed evidence of unusually prominent homocoupling. These defects could be suppressed by using brominated rather than iodinated monomers, more hindered 2,5-bis(tri-n-butylstannyl)thiophene as comonomer, and Pd2 dba3 /P(o-tol)3 as the catalyst at 100 °C. Under these conditions, macrocyclic species with n=3-10 repeating units formed preferentially according to MALDI-TOF MS analyses. Photophysical studies revealed a prominent effect of the regiochemistry and the nature of the pendent aryl groups on the absorption and emission, giving rise to orange, yellow-green, blue-green, and blue emissive materials respectively. The electronic effects were rationalized through DFT calculations on bis(terthiophene) model systems.

Highly Luminescent Ladderized Fluorene Copolymers Based on B-N Lewis Pair Functionalization.

A new B-N functionalized polyaromatic building block for conjugated hybrid polymers is developed. Bromine-functionalized dipyridylfluorene is first subjected to Lewis-base-directed electrophilic borylation and subsequently incorporated into conjugated polymers via transition-metal-catalyzed cross-coupling reactions. The borane monomer exhibits bright blue luminescence in solution, as a result of the rigid ladder-type structure generated upon electrophilic borylation. Yamamoto coupling gives rise to a homopolymer and Stille coupling to a vinylene-bridged copolymer. Polymerization of the BN-fused ladder molecules leads to large bathochromic shifts in absorption and emission, which are most pronounced for the vinylene-bridged copolymer. The polymers display strong luminescence in solution with quantum yields of 55% and 78% and sub-ns fluorescence lifetimes; the copolymer also exhibits bright yellow luminescence in the solid state when precipitated from solution.