Te-Li Exchange Reaction of Tellurophene-Containing π-Conjugated Polymer as Potential Synthetic Tool for Functional π-Conjugated Polymers.

Abstract

On the basis of the facts that tellurophene-containing π-conjugated polymers are obtainable from organotitanium polymers and that the tellurium atoms in the tellurophene derivatives can be transformed into lithium atoms, the synthesis of reactive lithiated polymer precursor and its transformations into some functionalized π-conjugated polymers are described. A regioregular organometallic polymer having 1,4-dilithio-1,3-butadiene and 9,9-dioctylfluorene-2,7-diyl units is generated by the reaction of a tellurophene-containing polymer having the number-average molecular weight (Mn ) and molecular weight distribution (Mw /Mn ) of 5890 and 1.9, respectively, with n-butyllithium (2.4 equiv.) at -78 °C to -60 °C for 3 h. The lithiated polymer thus prepared is subjected to reactions with electrophiles to produce functionalized π-conjugated polymers. For example, a π-conjugated polymer possessing 1,4-bis(tri-n-butylstannyl)-1,3-butadiene-1,4-diyl unit is obtained in 67% yield by the reaction with tri-n-butyltin chloride (2.4 equiv.) at -60 °C to ambient temperature for 12 h in tetrahydrofuran, whose Mn and Mw /Mn are estimated as 7320 and 2.5, respectively, by size exclusion chromatography. The absorption maximum and onset of the obtained polymer are observed at 380 and 465 nm, respectively, in the UV-vis spectrum, from which the optical band gap of the polymer is estimated as 2.67 eV.