Tunable [3+2] and [4+2] annulations for pyrrolidine and piperidine synthesis.

N-heterocycles are privileged pharmaceutical scaffolds in drug discovery and development. We disclose here divergent intermolecular coupling strategies that can access diverse N-heterocycles directly from olefins. The radical-to-polar mechanistic switching is key for the divergent cyclization processes. These distinctive annulations result in the coupling of alkenes with simple bifunctional reagents for divergent N-heterocycle syntheses.

Colloidal Nanoribbons: From Infrared to Visible.

Using the cation-exchange method, colloidal PbS nanoribbons are converted completely into CdS nanoribbons. This process expands the emission spectrum of the nanoribbons from infrared to visible. The morphology of nanoribbons remains the same after cation exchange, but the crystal structure changes from rock salt to zincblende. CdS nanoribbons exhibit blue band-edge photoluminescence under ultraviolet-light excitation. Cathodoluminescence spectroscopy of the CdS nanoribbons shows multicolor (blue, green, and red) emissions. Further time-resolved photoluminescence spectroscopy studies show that the lifetime of the midgap states is more than 2 orders of magnitude longer than that of the band-edge states.

Dielectrically Confined Stable Excitons in Few-Atom-Thick PbS Nanosheets.

Two-dimensional colloidal PbS nanosheets exhibit more than one order of magnitude larger exciton binding energy than their bulk counterpart, making it possible to generate stable excitons at room temperature. It is experimentally revealed that the binding energy of the exciton increases from 26 to 68 meV as the thickness of the PbS nanosheet decreases from 4.7 to 1.2 nm. The dielectric confinement of the exciton plays a critical role in the binding-energy enhancement. The large binding energy results in a fast thickness-dependent exciton radiative recombination rate, confirmed experimentally.

Using Interaction of Nano Dipoles to Control the Growth of Nanorods.

Charged facets of a nanocrystal can form an intrinsic nanometer-size electric dipole. When the spacing between these nano dipoles is adjusted, the dipolar interaction energy is tuned from a fraction to a multiple of the thermal energy. Consequently, the one-dimensional oriented attachment can be switched on or off, as is the growth of nanorods. This kinetically controlled growth is achieved at relatively low reaction temperatures while the thermodynamically controlled growth dominates at higher temperatures. The synthesized PbSe nanorods are branchless, exhibiting a single-exponential photoluminescence decay trace with an e-folding lifetime of 1.3 µs and a photoluminescence quantum yield of 35%.

Growth of colloidal PbS nanosheets and the enhancement of their photoluminescence.

Dual photoluminescence peaks observed during the synthesis of colloidal PbS nanosheets reveal their growth mechanism - two-dimensional attachments of the quantum dots. Well-grown nanosheets show the photoluminescence linewidth of 95 meV at room temperature. Aged nanosheets in toluene have enhanced photoluminescence with intensity improved by an order of magnitude.