Structural Properties of Highly Doped Borazino Polyphenylenes Obtained through Condensation Reaction.

Here we describe the synthesis and spectroscopic and structural characterization of various borazine-doped polyphenylenes displaying high doping dosages (16-18%). Capitalizing on the condensation reaction approach, the desired products were formed using a mixture of -phenylendiamine and aniline with BCl, followed by the addition of an aryl lithium derivative. The use of mesityl lithium (MesLi) yields strained multiborazine derivatives, which proved to be unstable in the presence of moisture.

Synthesis and Optoelectronic Properties of Hexa-peri-hexabenzoborazinocoronene.

The first rational synthesis of a BN-doped coronene derivative in which the central benzene ring has been replaced by a borazine core is described. This includes six C-C ring-closure steps that, through intramolecular Friedel-Crafts-type reactions, allow the stepwise planarization of the hexaarylborazine precursor. UV/Vis absorption, emission, and electrochemical investigations show that the introduction of the central BN core induces a dramatic widening of the HOMO-LUMO gap and an enhancement of the blue-shifted emissive properties with respect to its all-carbon congener.

Borazino-Doped Polyphenylenes.

The divergent synthesis of two series of borazino-doped polyphenylenes, in which one or more aryl units are replaced by borazine rings, is reported for the first time, taking advantage of the decarbonylative [4 + 2] Diels-Alder cycloaddition reaction between ethynyl and tetraphenylcyclopentadienone derivatives. Because of the possibility of functionalizing the borazine core with different groups on the aryl substituents at the N and B atoms of the borazino core, we have prepared borazino-doped polyphenylenes featuring different doping dosages and orientations. To achieve this, two molecular modules were prepared: a core and a branching unit.

Boron-nitrogen doped carbon scaffolding: organic chemistry, self-assembly and materials applications of borazine and its derivatives.

Discovered by Stock and Pohland in 1926, borazine is the isoelectronic and isostructural inorganic analogue of benzene, where the C[double bond, length as m-dash]C bonds are substituted by B-N bonds. The strong polarity of such heteroatomic bonds widens the HOMO-LUMO gap of the molecule, imparting strong UV-emitting/absorption and electrical insulating properties. These properties make borazine and its derivatives valuable molecular scaffolds to be inserted as doping units in graphitic-based carbon materials to tailor their optoelectronic characteristics, and specifically their semiconducting properties.