A series of novel amidinate ligated four-coordinated boron compounds, [(Ar)-C(BuN)BF] (1BF2-6BF2), were synthesised and structurally characterised (Ar = 1-phenyl, 2-naphthyl, 2-anthryl, 9-anthryl, 9-phenanthryl and 1-pyrene). The increased π-conjugation of Ar-substitution on the amidinate ligand results in dark blue-emission in compounds 3BF2-6BF2. All these compounds are emissive in the solution state. The 2-anthryl substituted compound 3BF2 was found to exhibit a maximum quantum yield of 48% in dichloromethane. Theoretical studies were carried out which validate the hypothesis about the increased π-conjugation.
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