Using boryl-substitution and improved Suzuki-Miyaura cross-coupling to access new phosphorescent tellurophenes.

Abstract

A new di(isopropoxy)boryl -B(OiPr)2 tellurophene precursor is described, from which several previously inaccessible phosphorescent borylated tellurophenes are formed via exchange of the -OiPr groups. One such tellurophene Mes(iPrO)B-Te-6-B(OiPr)Mes, bearing a sterically encumbered mesityl (Mes) substituent at each boron center, exhibits bright yellow-orange phosphorescence in the solid state at room temperature and in the presence of the known quencher O2. Furthermore, Suzuki-Miyaura cross-coupling between the newly prepared borylated tellurophenes and the test substrate 2-bromothiophene was examined with the pre-catalyst Cl(XPhos)Pd(aminobiphenyl). While more electron deficient boryl groups such as catecholatoboryl (-Bcat) yield significant protodeboronation in place of productive C-C bond formation, efficient formation of the desired thiophene-capped tellurophene thienyl-Te-6-thienyl was noted from tellurophenes bearing the readily accessible pinacolatoboryl (-Bpin) and 1,8-naphthalenediaminatoboryl (-Bdan) functional groups. These findings open the door for the efficient synthesis of aryl tellurophenes and polytellurophenes via the ubiquitous Suzuki-Miyaura coupling of borylated tellurophenes, which was previously hampered by protodeboronation.