Scanning-tunneling-microscope-induced light emission serves as a powerful approach in revealing and manipulating the optical properties of molecular species, intermolecular energy transfer, and plasmon-molecule coupling. Earlier studies have established the existence of molecular up-conversion electroluminescence in diverse situations, but the underlying microscopic mechanisms are still under active debate, dominated by intermolecular triplet-triplet annihilation and plasmonic pumping. Here we report on the experimental realization of up-conversion electroluminescence from a prototypical single phthalocyanine molecule, allowing us to unambiguously rule out mechanisms based on intermolecular coupling and also offering unprecedented opportunities to elucidate much richer characteristics unforeseen in previous studies. In particular, the bias-dependent emission intensity displays three distinct regions with different nonlinear current dependences, which can be attributed to crossover behavior caused by the interplay between inelastic electron scattering and carrier-injection processes. We also develop a microscopic description to capture the essential physics involved in up-conversion electroluminescence mediated by a proper intermediate spin-triplet state.

Spirocycles play an important role in drug discovery and development. The direct, catalytic, and enantioselective synthesis of spirocycles from readily available starting materials and in an atom economic manner remains a highly sought-after task in organic synthesis. Herein, an enantioselective Pd-hydride-catalyzed cycloaddition method for the synthesis of spirocyclic compounds directly from two classes of commonly available starting materials, 1,3-enynes and cyclic carbon−hydrogen (C−H) bonds, is reported. The reactions employ a chiral Pd/WingPhos catalyst to both suppress the formation of bis-allenyl by-products and control the stereoselectivity. 1,3-Enynes are used as dielectrophilic four-carbon units in the cycloaddition reactions, which also enables an enyne substrate-directed enantioselectivity switch with good levels of stereocontrol. The present spirocycle synthesis tolerates a broad range of functional groups of 1,3-enyne substrates, including alcohols, esters, nitriles, halides, and olefins. A variety of diverse cyclic nucleophiles, including pharmaceutically important heterocycles and carbocycles, can be flexibly incorporated with spiro scaffolds.