Blue emissive amidinate-based tetra-coordinated boron compounds.

A series of novel amidinate ligated four-coordinated boron compounds, [(Ar)-C(tBuN)2BF2] (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.

Boron-Thioketonates: A New Class of S,O-Chelated Boranes as Acceptors in Optoelectronic Devices.

Development of new n-type semiconductors with tunable band gap and dielectric constant has significant implication in dissociating bound charge carrier relevant for demonstrating high performance optoelectronic devices. Boron-ß-thioketonates (MTDKB), analogues to boron-ß-diketonates containing a sulfur atom in the framework of ß-diketones were synthesized. Bulk transport measurement exhibited an outstanding bulk electron mobility of ≈0.003 cm2 V-1 s-1 , which is among the best values reported till date in these class of semiconducting materials and correspondingly a single junction photo responsivity of upto 6 mA W-1 was obtained. This new family of O,S-chelated boron compounds exhibited luminescence in the far red/near-infrared region. The remarkable red shift of 89 nm (fluorescence) observed for 4 a in comparison with analogues boron-ß-diketonate signifies the importance of sulfur in these molecules. MTDKBs with amine functionality have also been investigated as an ON/OFF fluorescent sensor.

Tetra-Coordinated Boron-Functionalized Phenanthroimidazole-Based Zinc Salen as a Photocatalyst for the Cycloaddition of CO2 and Epoxides.

A unique B-N coordinated phenanthroimidazole-based zinc salen was synthesized. The zinc salen thus synthesized acts as a photocatalyst for the cycloaddition of carbon dioxide with terminal epoxides under ambient conditions. DFT study of the cycloaddition of carbon dioxide with terminal epoxide indicates the preference of the reaction pathway when photocatalyzed by zinc salen. We anticipate that this strategy will help to design new photocatalysts for CO2 fixation.

Recent advances in the synthesis of luminescent tetra-coordinated boron compounds.

Tetra-coordinated boron compounds offer a plethora of luminescent materials. Different chelation around the boron center (O,O-, N,C-, N,O-, and N,N-) has been explored to tune the electronic and photophysical properties of tetra-coordinated boron compounds. A number of fascinating molecules with interesting properties such as aggregation induced emission, mechanochromism and tunable emission by changing the solvent polarity were realised. Owing to their rich and unique properties, some of the molecules have shown applications in making optoelectronic devices, probes and so on. This perspective provides an overview of the recent developments of tetra-coordinated boron compounds and their potential applications.

Thiophene-fused boracycles as photoactive analogues of diboraanthracenes.

The construction of thiophene-fused analogues of diboraanthracenes with different aryl substituents through boron-mercury exchange followed by the nucleophilic replacement of the chlorines of dichlorodiboradithiophene 2 with Grignard reagents is reported. These diboradithiophenes exhibited unusual photophysical and electrochemical properties. They all undergo photoisomerisation, which can be traced using photophysical and 1H NMR spectroscopy studies.

Synthesis of π-extended B ← N coordinated phenanthroimidazole dimers and their linear and nonlinear optical properties.

Intramolecular B ← N coordinated fluorophores have shown potential applications in optoelectronics and as sensors due to their unique photophysical properties. In this work, we report the synthesis and characterization of π-conjugated boron doped phenanthroimidazole dimers. All the π-conjugated B ← N coordinated phenanthroimidazole dimers exhibited high quantum yields in solution (up to 99%) and moderate quantum yields in the solid state (up to 51%). We investigated the nonlinear optical properties of phenanthroimidazole dimers and found that the measurement of two-photon-absorption cross-section is correlated with the conjugation length.