Generation and electronic properties of lanthanide–cyclooctatetraene organometallic clusters in gas phase

Abstract

Organometallic clusters of lanthanide (Ln = Nd, Er, Eu, and Yb) and 1,3,5,7-cyclooctatetraene (C 8 H 8 ) were produced by a combination of laser vaporization and molecular beam methods. In the mass spectra of [Lnn(C 8 H 8 )m], compositions of m = n + 1 were magic numbers. From mass spectrometry, photoionization spectroscopy, and photoelectron spectroscopy, we have concluded that these magic-numbered clusters take multiple-decker sandwich structures in which Ln atoms and C 8 H 8 molecules are alternatedly piled up. These sandwich clusters are formed through ionic bonds composed of multiply charged cations [Ln k+ (k = 2 and 3)] and multiply charged anions [C 8 H h− 8 (h = 1, 1.5, and 2)].PACS. 36.40.-c Atomic and molecular clusters -36.40.Mr Spectroscopy and geometrical structure of clusters -61.46.+w Clusters, nanoparticles, and nanocrystalline materials -71.24.+q Electronic structure of clusters and nanoparticles

Anti-Bimetallic Complexes of Divalent Lanthanides with Silylated Pentalene and Cyclooctatetraenyl Bridging Ligands as Molecular Models for Lanthanide-Based Polymers

“…Considerable development toward a controlled synthesis of the COT-bridged chains has been recently achieved by use of laser vaporization techniques and molecular beam methods and has allowed the characterization of the oligomeric materials [Eu(COT)] n and Ln n (COT) n +1 (Ln = Ce, Nd, Eu, Ho, Yb, Tm, Tb), with chain lengths of up to n = 18 for Eu (giving nanowires up to 8 nm in length). − In situ studies have given some evidence for intramolecular M−M interactions but have only provided a partial insight into the properties of these systems; due to low solubility these polymers are difficult to manipulate and study in the laboratory by conventional methods.…”

Laser Plasma Production of Metal and Metal Compound Complexes with Polycyclic Aromatic Hydrocarbons

“…5,6 In addition, Kaya and co-workers have produced sandwich complexes of metals with cyclooctatetraene (COT). 7 Other metal-fullerene complexes have been produced and studied by Martin and co-workers, [8][9][10][11] by Kaya and co-workers, [12][13][14][15] and by our research group. 16, 17 Martin and co-workers were able to produce multiatom coatings of transition metals on C 60 or C 70 using an inert gas condensation source employing laser vaporization and a fullerene oven.…”

Wavelength Dependent Photofragmentation Patterns of Tris(2,2,6,6-tetramethyl-3,5-heptanedionato)Ln (III) (Ln = Eu, Tb, Gd) in a Molecular Beam

“…The gas-phase photofragmentation of metal-containing compounds is of interest because of its importance in understanding laser-assisted chemical vapor deposition. − Only a few photochemical studies of lanthanide-based precursors in the gas phase have been reported, − in contrast to substantial work on transition-metal complexes. − …”

“…The gas-phase photofragmentation of metal-containing compounds is of interest because of its importance in understanding laser-assisted chemical vapor deposition. [1][2][3][4][5] Only a few photochemical studies of lanthanide-based precursors in the gas phase have been reported, [6][7][8][9][10][11][12][13][14] in contrast to substantial work on transition-metal complexes. [15][16][17][18][19][20][21][22] In a study of photoionization mass spectrometry of Eu(thd) 3 in a molecular beam, 266 nm nanosecond pulsed-laser excitation produced a mass spectrum dominated by bare europium ions and ligand fragments.…”