[Sm6O4(cbz)10(thf)6]·2C7H8: A Polynuclear Samarium Oxo Cluster Obtained from Carbazole-Driven Oxidation of Samarium Nanoparticles.

Zerovalent samarium nanoparticles (1.7 ± 0.2 nm in size) are used as the starting material to prepare single crystals of the novel polynuclear samarium oxo cluster [Sm6O4(cbz)10(thf)6]·2C7H8. The reaction is performed by oxidation with carbazole (CbzH) in tetrahydrofuran (THF) at 50 °C with subsequent crystallization in toluene (C7H8). The oxo cluster contains noncharged molecular units with a central Sm6O4 core. Single-crystal structure analysis and infrared spectroscopy confirm the oxidation of CbzH with the formation of (cbz)-. Polynuclear carbazole complexes are generally rare and here prepared using metal nanoparticles as a reactive starting material for the first time. The reaction with CbzH as a sterically demanding ligand exemplarily shows the feasibility of rare-earth-metal nanoparticles for obtaining new compounds with complex composition and structure.

Liquid-Phase Synthesis of Highly Reactive Rare-Earth Metal Nanoparticles.

The first liquid-phase synthesis of high-quality, small-sized rare-earth metal nanoparticles (1-3 nm)-ranging from lanthanum as one of the largest (187 pm) to scandium as the smallest (161 pm) rare-earth metal-is shown. Size, oxidation state, and reactivity of the nanoparticles are examined (e.g., electron microscopy, electron spectroscopy, X-ray absorption spectroscopy, selected reactions). Whereas the nanoparticles are highly reactive (e.g. in contact to air and water), they are chemically stable as THF suspensions and powders under inert conditions. The reactivity can be controlled to obtain inorganic and metal-organic compounds at room temperature.

18-Crown-6 Coordinated Metal Halides with Bright Luminescence and Nonlinear Optical Effects.

The crown-ether coordination compounds ZnX2(18-crown-6), EuX2(18-crown-6) (X: Cl, Br, I), MnI2(18-crown-6), Mn3Cl6(18-crown-6)2, Mn3I6(18-crown-6)2, and Mn2I4(18-crown-6) are obtained by ionic-liquid-based synthesis. Whereas MX2(18-crown-6) (M: Zn, Eu) show conventional structural motives, Mn3Cl6(18-crown-6)2, Mn3I6(18-crown-6)2, and Mn2I4(18-crown-6) exhibit unusual single MnX4 tetrahedra coordinated to the crown-ether complex. Surprisingly, some compounds show outstanding photoluminescence. Thus, rare Zn2+-based luminescence is observed and unexpectedly efficient for ZnI2(18-crown-6) with a quantum yield of 54%. Unprecedented quantum yields are also observed for Mn3I6(18-crown-6)2, EuBr2(18-crown-6), and EuI2(18-crown-6) with values of 98, 72, and 82%, respectively, which can be rationalized based on the specific structural features. Most remarkable, however, is Mn2I4(18-crown-6). Its specific structural features with finite sensitizer-activator couples result in an extremely strong emission with an outstanding quantum yield of 100%. Consistent with its structural features, moreover, anisotropic angle-dependent emission under polarized light and nonlinear optical (NLO) effects occur, including second-harmonic generation (SHG). The title compounds and their optical properties are characterized by single-crystal structure analysis, X-ray powder diffraction, chemical analysis, density functional theory (DFT) calculations, and advanced spectroscopic methods.