Synthesis and Thin Films of Thermally Robust Quartet (S = 3/2) Ground State Triradical.

High-spin (S = 3/2) organic triradicals may offer enhanced properties with respect to several emerging technologies, but those synthesized to date typically exhibit small doublet quartet energy gaps and/or possess limited thermal stability and processability. We report a quartet ground state triradical 3, synthesized by a Pd(0)-catalyzed radical-radical cross-coupling reaction, which possesses two doublet-quartet energy gaps, ΔEDQ ≈ 0.2-0.3 kcal mol-1 and ΔEDQ2 ≈ 1.2-1.8 kcal mol-1. The triradical has a 70+% population of the quartet ground state at room temperature and good thermal stability with onset of decomposition at >160 °C under an inert atmosphere. Magnetic properties of 3 are characterized by SQUID magnetometry in polystyrene glass and by quantitative EPR spectroscopy. Triradical 3 is evaporated under ultrahigh vacuum to form thin films of intact triradicals on silicon substrate, as confirmed by high-resolution X-ray photoelectron spectroscopy. AFM and SEM images of the ∼1 nm thick films indicate that the triradical molecules form islands on the substrate. The films are stable under ultrahigh vacuum for at least 17 h but show onset of decomposition after 4 h at ambient conditions. The drop-cast films are less prone to degradation in air and have a longer lifetime.

Self-aligned placement and detection of quantum dots on the tips of individual conical plasmonic nanostructures.

Hybrid structures of few or single quantum dots (QDs) coupled to single optical antennas are of prime interest for nano-optical research. The photoluminescence (PL) signal from single nanoemitters, such as QDs, can be enhanced, and their emission characteristics modified, by coupling them to plasmonic nanostructures. Here, a self-aligned technique for placing nanoscale QDs with about 10 nm lateral accuracy and well-defined molecular distances to the tips of individual nanocones is reported. This way the QDs are positioned exactly in the high near-field region that can be created near the cone apex. The cones are excited in the focus of a radially polarized laser beam and the PL signal of few or single QDs on the cone tips is spectrally detected.