Once considered as mere curiosities, acyl metalloids are now recognized for their useful enabling in chemical synthesis. This perspective considers the reactivity displayed by acylboron, -silicon, -germanium, and tellurium species....

Conjugated polymers have received widespread interest as optoelectronic materials. Recently, these macromolecules have been adopted for biologically relevant applications, such as sensors, imaging agents, and drug delivery vectors. A major limitation of the chemistry used to prepare these classes of compounds is that the resultant polymers themselves are not tolerant to water or are not inherently water-soluble. For example, the most controlled method of conjugated polymer synthesis, the Kumada catalyst transfer polymerization (KCTP), requires stringent drying of monomers, catalysts, and other reagents. Here, we describe an approach to use a water-scavenging Grignard reagent to alleviate many of the shortcomings that currently hinder the synthesis of water-soluble conjugated polymers. This method shows improved polymerization performance in both traditional conjugated polymer synthesis as well as more challenging syntheses of polar hygroscopic polymers that are of interest for biological applications.

Sodium cyanoborohydride-derived N-alkyl­nitrilium­boranes were found to be versatile precursors for the synthesis of novel boron-containing heterocycles. The reaction between N-alkyl­nitrilium­boranes and 2-aminopyridines, imidazoles, oxazoles, or isoxazoles leads to the incorporation of the [B–C] motif into a five-membered boramidine, which exists as a mixture of Z and E isomers. The resulting heterocycles are blue fluorescent in both the solid state and in solution with ca. 2700–8400 cm–1 Stokes shifts and quantum yields in the 65–74% range in water and in the 42–84% range in organic solvents. The combination of photophysical properties, structural tunability, stability, and solubility in various media is expected to find application in a range of disciplines.

Here we demonstrate an approach to graft bis-(heteroaryl)-containing motifs into ring structures. The process occurs by redirecting a previously reported oxadiazole-forming reaction towards a pyrazole-forming process affording pyrazolyl-azole containing molecules. Through the use of (N-isocyan-[a] C.

A new boron-containing heterocyclic scaffold – borindolizine – is reported as a new heterocyclic scaffold with broadly tunable fluorescence and a high Stokes shift. Two classes of emitters were synthesized through rational scaffold changes resulting in blue-emitting carboxyborindolizines (λmax,em = 431 – 459 nm) and green emitting aryl borindolizines (λmax,em = 488 – 519 nm). Experimental structure-emission trends were used to validate a computational spectral prediction model and subsequently used to design a red-emissive fluorophoric scaffold. A red-emissive (λmax,abs = 370 nm, λmax,em = 635 nm) isoquinolyl borinidolizine was synthesized in excellent agreement with the theoretical emission (λmax,em = 621 nm). These results establish borindolizine as a highly attractive class of fluorescent heterocycle with a highly tunable emission, allowing for custom fluorophore synthesis.