A comprehensive overview of advances in the synthesis of organoborane polymers for optical, electronic, and sensory applications, is presented. Study of conjugated main chain organoboron polymers obtained through hydroboration of 2,5-diethynylthiophene derivatives with BCl3/Et3SiH mixture showed that polymers are differently colored depending on the substituents on the alkynyl groups. Luminescent polymer gels prepared by hydroboration polymerization of MesBH2 showed the occurrence of partial gelation when the reaction is performed in relatively concentrated THF solution. Tin-boron exchange reactions are also studied as a potentially milder and more selective polymerization method showing that the polycondensation process occurs between a bifunctional haloborane and a ditin species.
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