A General Protocol for the Polycondensation of Thienyl N‑Methyliminodiacetic Acid Boronate Esters To Form High Molecular Weight Copolymers

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Abstract

Thienyl di-MIDA boronate esters are readily synthesized
by electrophilic C-H borylation producing bench stable crystalline
solids in good yield and excellent purity. Optimal conditions
for the slow release of the boronic acid using KOH as the base in
biphasic THF/water mixtures enables the thienyl MIDA boronate
esters to be extremely effective homo-bifunctionalized (AA-type)
monomers in Suzuki-Miyaura co-polymerizations with dibromoheteroarenes
(BB-type monomers). A single polymerization protocol
is applicable for the formation of five alternating thienyl copolymers
that are (or are close analogues of) state of the art materials
used in organic electronics. The five polymers were produced in
excellent yields and with high molecular weights comparable to
those produced using Stille co-polymerization protocols. Therefore
thienyl di-MIDA boronate esters represent bench stable / low toxicity
alternatives to highly toxic di-trimethylstannyl AA-type monomers
that are currently ubiquitous in the synthesis of these important
alternating copolymers.

Bibliographical metadata

Original languageEnglish
Pages (from-to)13361-13368
Number of pages8
JournalJournal of the American Chemical Society
Volume138
Issue number40
Early online date16 Sep 2016
DOIs
StatePublished - 12 Oct 2016