IZCp and PZCp: Redox Non-innocent Cyclopentadienyl Ligands as Electron Reservoirs for Sandwich Complexes.

A long-sustained effort of systematic steric and electronic modification of cyclopentadienyl (Cp) ligands has enabled them to find wide-ranging, valuable applications. Herein, we present two novel Cp ligands: imidazolium- and pyrrolinium-substituted zwitterionic Cps (IZCp and PZCp), whose key utility is redox non-innocence─the ability to participate cooperatively with the metal center in redox reactions. Through the simple metalation of ZCps, the Cr(0) and Mo(0) half-sandwich complexes (IZCp)Cr(CO)3, (PZCp)Cr(CO)3, (IZCp)Mo(CO)3, and (PZCp)Mo(CO)3, respectively, as well as the Ru(II) sandwich complexes [(IZCp)RuCp]PF6 and [(PZCp)RuCp]PF6 were prepared. The sandwich complexes were fully characterized and showed by cyclic voltammetry reversible one-electron reduction at E1/2 potentials ranging from -1.7 to -2.7 V vs Fc/Fc+. These values are unusually low and have not been observed with other Cp ligands due to the instability of the reduced complexes. Density functional theory (DFT) calculations for the reduced sandwich derivatives with IZCp and PZCp showed their spin densities to be highly delocalized over their ZCp ligand moieties (70-90%). Electron paramagnetic resonance (EPR) analysis of the isolated K[(PZCp)Mo(CO)3] and (PZCp)RuCp also indicated a high degree of ligand-localized radical character. Thus, the IZCp and PZCp ligands act as electron reservoirs to sustain these sandwich complexes in highly reduced states. At the same time, the CO stretching frequencies of K[(PZCp)Mo(CO)3]: νCO 1871, 1748, and 1699 cm-1, rank the [PZCp]- ligand as the strongest electron-donating Cp ligand among the reported CpMo(CO)3 derivatives, whose νCO > 1746 cm-1. In addition, these redox non-innocent Cps were obtained in high yields and found to be practically air- and moisture-stable, unlike typical Cps.

Formation of Highly Stable 1,2-Dicarbonyl Organic Radicals from Cyclic (Alkyl)(amino)carbenes.

Two air-stable organic radicals derived from oxalyl chloride and cAAC were synthesized, resulting in the unexpected formation of a known (amino)(carboxy) radical cation ([2]BF4) and the oxidative formation of a 1,2-dicarbonyl radical cation ([3]BF4) from a neutral 3-oxetanone compound (4). The highly strained and newly discovered 4 was obtained by a single-electron reduction of [3]BF4 with a mild reducing agent. This result differs from the generation of NHC-based 1,2-dicarbonyl radicals, indicating the uniqueness of cAAC.

Critical nanofocusing of magnetic dipole moment using a closed plasmonic tip.

Squeezing magnetic dipole (MD) moment into a deep subwavelegnth apex of a tapered tip has not been achieved so far owing to a specific mode volume of a MD resonance which is dependent on an operating wavelength and back reflection of nanofocused waves. We propose a novel strategy for efficient delivery and nanofocusing of optical MD at an apex of a closed resonant plasmonic tip. Due to the ultracompact area (~λ2/900) of the nanocavity and resonances assisted by partial mirrors in a plasmonic waveguide, the enhancement factor of magnetic energy density is improved over 5 times. We expect that our scheme can help to investigate strong magnetic phenomena, including enhanced magnetic transition, artificial optical magnetism, multipole nonlinear optics, biomolecular sensing, magnetic near-field imaging, and spectroscopy.