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A new class of highly fluorescent triarylborane polymers has been prepared from trimethylsilyl-substituted polystyrene via a modular approach that involves selective polymer modification reactions with organometallic reagents. The photophysical properties, environmental stability, and the Lewis acidity of the boron sites have been tailored through modifications in the substitution pattern on boron. The photophysical properties are indicative of electronic communication between the chromophores attached to polystyrene, which has been exploited for the efficient probing of fluoride and cyanide in the micromolar concentration range.

Iron chains: The highly soluble, ferrocene‐containing polymer [‐fc‐B(Mes)‐]n (fc=Fe(C5H4)2, Mes=mesityl), with an average chain length of about 16 repeat units (n=16), is readily accessible by a novel polycondensation reaction starting from fc(BBr2)2 and HSiEt3 (see scheme). The polymer contains three‐coordinate boron centers, which are well‐suited for the promotion of electron delocalization along the polymer chain.

Building bridges: The title compound forms an unprecedented polymeric structure with bridging B-H-B three-center two-electron bonds in the solid state. This organoborane serves as an efficient precursor for the preparation of boron-doped pi-conjugated polymers by hydroboration polymerization with a functionalized 1,4-diethynylbenzene (see picture). These polymers form thin films that show intense green luminescence.