The effect of ethynylene or ethynylene-thiophene spacers on the band gap of alternating polymers, containing 4,9-naphthothiadiazole units as an acceptor and 2,7-linked fluorene repeat units as a donor, were investigated. The Sonogashira coupling reaction was employed to prepare the two novel copolymers, namely ((9,9-dioctyl-fluorene)-2,7-diethynylene-alt-4,9-2,1,3-naphthothiadiazole (PFDENT) and poly(5,5'-(9,9-dioctyl-fluorene-2,7-diyl)bis(ethynyl-2-thienyl)-alt-4,9-(2,1,3-naphthothiadiazole) (PFDTENT). The optical, electrochemical and thermal properties of the two obtained polymers were widely investigated and compared. Both resulting polymers showed low solubility in common organic solvents and moderate molecular weights. It is believed that the introduction of acetylene linkers rather than acetylene-thiophene spacers on the polymer chains reduces the steric hindrance between the donor and acceptor units which leads to the adoption of more planar structures of polymeric chains, resulting in decreased molecular weights of the resulting conjugated polymers. Thus, both ethynylene-based polymers and ethynylene-thiophene-based polymers showed red-shifted absorption maxima compared to their counterpart (thiophene-based polymer), owing to the adoption of more planar structures. Optical studies revealed that the new ethynylene and ethynylene-thiophene-based polymers displayed low band gaps compared to their thiophene analogue polymer PFDTNT. Both resulting polymers showed good thermal stability. X-ray diffraction (XRD) patterns of both polymers revealed that PFDENT and PFDTENT possessed an amorphous nature in solid state.
Keywords: XRD study; conjugated polymers; naphthothiadiazole (NT); optical properties; thermal analysis.