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Poly(<i>p</i>‑phenylenediethynylene phosphine)s and Related π‑Conjugated Phosphine–Diyne Polymers: Synthesis, Characterization and Photophysical Properties
Despite
the considerable synthetic challenge, polymers that incorporate
phosphorus atoms within or adjacent to a π-conjugated backbone
framework are of interest due to the ability to modulate the photophysical
properties of the polymer based on the chemical environment at phosphorus.
We report the synthesis and characterization of polyÂ(<i>p</i>-phenylenediethlynylene phosphine)Âs, <b>1a</b>–<b>1e</b>, a new class of σ–π conjugated polymer.
Polymers <b>1a</b>–<b>1e</b> were prepared by a
Ni-catalyzed coupling of dialkynes with phenyldichlorophosphine in
the presence of excess triethylamine and have molecular weights (<i>M</i><sub>w</sub>) up to 12,000 g mol<sup>–1</sup> (vs.
polystyrene). While the polymers <b>1b</b>–<b>1e</b> are nonfluorescent, blue fluorescence is observed upon oxidation
of the phosphorus centers (Φ<sub>soln</sub> = 0.12–0.28).
Polymers <b>1b</b>·O–<b>1e</b>·O also
exhibit yellow/green fluorescence in the solid state (Φ<sub>solid</sub> = 0.04–0.08). These results introduce a fascinating
new class of main group-containing macromolecule and lay the groundwork
for their utilization in sensory applications and/or their incorporation
into optoelectrical devices