We have achieved substitutional doping of ullazine with either two BO units or with one BO unit and one BN unit. The synthesis of these B-doped ullazines is straightforward, using demethylation and borylative cyclization as the key steps. Ullazine cores of both BN/BO-ullazines (2) and bis-BO-ullazines (3) are very close to being planar. Their electronic and photophysical properties were investigated by ultraviolet− visible, fluorescence spectroscopy, cyclic voltammetry, and density functional theory calculations.

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Boron/nitrogen-doped fluoranthenes, a new class of BN-doped cyclopenta-fused polycyclic aromatic hydrocarbons, were synthesized via pyrrolic-type nitrogen directed C−H borylation. Regioselective bromination of BN-fluoranthene (3a) gave mono-and dibrominated BN-fluoranthenes. The halogenated BN-fluoranthene (3b) can undergo various of further crosscoupling reactions to deliver a series of BN-fluoranthenes. Moreover, incorporating BN unit in to fluoranthene resulted in a wider HOMO−LUMO energy gaps. The aromaticities of the BN-fluoranthene (3a) were quantified by experimental and computational studies.

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Empowering conventional materials with unexpected magnetoelectric properties is appealing to the multi‐functionalization of existing devices and the exploration of future electronics. Recently, owing to its unique effect in modulating a matter's properties, ultra‐small dopants, for example, H, D, and Li, attract enormous attention in creating emergent functionalities, such as superconductivity, and metal–insulator transition. Here, an observation of bipolar conduction accompanied by a giant positive magnetoresistance in D‐doped metallic Ti oxide (TiOxDy) films is reported. To overcome the challenges in intercalating the D into a crystalline oxide, a series of TiOxDy is formed by sequentially doping Ti with D and surface/interface oxidation. Intriguingly, while the electron mobility of the TiOxDy increases by an order of magnitude larger after doping, the emergent holes also exhibit high mobility. Moreover, the bipolar conduction induces a giant magnetoresistance up to 900% at 6 T, which is ≈6 times higher than its conventional phase. This study paves a way to empower conventional materials in existing electronics and induce novel electronic phases.