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

Kurikawa, Tsuyoshi; Hayakawa, F.; Nagao, Shigeaki; Miyajima, Ken; Nakajima, Atsushi; Kaya, Kunimitsu

doi:10.1007/978-3-642-88188-6_54

Cited by 12 publications

(17 citation statements)

References 21 publications

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“…25 In the formation of LnCOT anions, larger clusters of (n, n + 1) ¹ at n > 2 could be produced only for Eu and Yb, while (1,2) ¹ was mainly produced for Ce, Nd, and Ho. This can be explained by the electronic structure, which will be discussed later.…”

Section: Anion Pe Spectra For [Ln(cot) 2 ]mentioning

confidence: 95%

“…When benzene (Bz) and 1,3,5,7-cyclooctatetraene (COT) vapor was injected for V and Eu vaporization, the organometallic clusters of V n (Bz) m and Eu n (COT) m were formed, respectively. 19,20,25 2.1.3 Giant Molecular Clusters: By means of supersonic expansion of a mixture of molecules diluted in a carrier gas (typically a noble gas), both an efficient cooling and formation of molecular clusters is easily realized in the gas phase. To increase the total number of collisions between seed molecules during expansion, it is necessary to obtain a reasonable vapor pressure of sample of interest by heating both the sample reservoir and the valve.…”

Section: Composite Organometallic Clustersmentioning

confidence: 99%

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Study on Electronic Properties of Composite Clusters toward Nanoscale Functional Advanced Materials

Nakajima

2013

Bulletin of the Chemical Society of Japan

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Clusters consisting of 101000 atoms size-dependently exhibit novel electronic and geometric properties. In particular, composite clusters composed of several elements and/or components provide a promising way for a bottom-up approach for designing functional advanced materials, because the functionality of the composite clusters can be optimized not only by the cluster size but also by their compositions. This account surveys recent investigations of composite clusters focusing on the efforts to create a new functional composite cluster by a fine doping or hybridization based on their size-specific electronic properties. Organometallic clusters and caged clusters are demonstrated as a representative example of designing the functionality of magnetism and electronic state structures. In order to create functional nanomaterials, furthermore, a fine controlling methodology of the soft-landing technique has been developed to fix the composite clusters onto a surface decorated with a self-assembled monolayer. The embedded isolation mechanism on the substrate is discussed form the viewpoint of self-assembly phenomena with the molecular ordering of ·· interaction, and also the electronic structures characterized by molecular ordering of ³³ interaction is intrinsically revealed by molecular clusters of ³-conjugate polyacenes as a model for self-assembled aggregates.

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Section: Anion Pe Spectra For [Ln(cot) 2 ]mentioning

confidence: 95%

Section: Composite Organometallic Clustersmentioning

confidence: 99%

Study on Electronic Properties of Composite Clusters toward Nanoscale Functional Advanced Materials

Nakajima

2013

Bulletin of the Chemical Society of Japan

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“…Twelve Ln complexes from La to Lu (excluding Pm, Eu, and Yb) were prepared in this manner. Among the excluded species, Pm is radioactively unstable, and therefore is not available commercially, and Eu and Yb preferentially adopt the +2 over the +3 oxidation state, as previously reported. − To record the PE spectra of the 12 Ln–COT species, cluster anions were coaxially extracted by a pulsed electric field of −3.0 and −1.5 keV in mass analysis and PE spectroscopy measurements, respectively. Once the cluster beam had decelerated, the mass-selected anion clusters were photodetached by a Nd 3+ : YAG laser pulsed at the third harmonic (355 nm, 3.49 eV), fourth harmonic (266 nm, 4.66 eV), and fifth harmonic (213 nm, 5.82 eV).…”

Section: Experimental Sectionmentioning

confidence: 99%

Investigation of the Electronic Structures of Organolanthanide Sandwich Complex Anions by Photoelectron Spectroscopy: 4f Orbital Contribution in the Metal–Ligand Interaction

et al. 2014

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The electronic structures of lanthanide (Ln) ions sandwiched between 1,3,5,7-cyclooctatetraene (COT), Ln(COT)2(-), have been investigated by anion photoelectron spectroscopy. Complexes of 12 Ln atoms were investigated (excluding promethium (Pm), europium (Eu), and ytterbium (Yb)). The 213 nm photoelectron (PE) spectra of Ln(COT)2(-) exhibit two peaks assignable to the highest occupied molecular orbital (HOMO; e2u) and the next HOMO (HOMO-1; e2g) approximately at 2.6 and 3.6 eV, respectively, and their energy gap increases as the central metal atom progresses from lanthanum (La) to lutetium (Lu). Since lanthanide contraction shortens the distance between the Ln atom and the COT ligands, the widening energy gap represents the destabilization of the e2u orbital as well as the stabilization of the e2g orbital. Evidence for 4f orbital contribution in the metal-ligand interaction has been revealed by the Ln atom dependence in which the same e2u orbital symmetry enables an interaction between the 4f orbital of Ln atoms and the π orbital of COT.

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“…Among them, two kinds of typical organometallic sandwich complexes have been extensively studied: 3d-transition metal (TM)–organic ligand (OL) (e.g., OL = benzene, Bz = C 6 H 6 ; naphthalene, Np = C 8 H 10 ; cyclopentadienide, Cp = C 5 H 5 , etc.) and 4f-lanthanide metal (Ln)–OL (OL = cyclooctatetraene, COT = C 8 H 8 ) sandwich complexes, Eu n COT m and Ho n COT m , etc., − and great advances have been made: (i) Experimentally, up to 7-layer V n Bz m and 18-layer Eu n COT m are successfully synthesized in gas by the laser vaporization method. , (ii) Size-dependent magnetic moments (MMs) are identified for V n Bz m and Eu n COT m , in terms of molecular beam magnetic resonance methods and theoretical calculations. , (iii) One-dimensional (1D) infinite sandwich molecular wires (ISMWs), e.g., [BzV] ∞ , [BzMn] ∞ , [CpV] ∞ , [CpCr] ∞ , etc., are expected to be ferromagnetic half metals (FM HMs) with only one spin channel electron at the Fermi energy, and such properties support their promising applications in spin electronics. , …”

Section: Introductionmentioning

confidence: 99%

Tunable Electronic and Magnetic Properties of Boron/Nitrogen-Doped BzTMCpTMBz/CpTMCpTMCp Clusters and One-Dimensional Infinite Molecular Wires

et al. 2014

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We systematically studied the structural, electronic, and magnetic properties of B/N-doped BzTMCp*TMBz/ CpTMCp*TMCp (Bz = C 6 H 6 ; Cp = C 5 H 5 ; Cp* = C 5−x D x H 5 ; D = B, N; x = 1, 2; TM = V, Cr, Mn, Fe) sandwich clusters and their infinite molecular wires using first-principle calculations. It is found that the B/N-doped ligands do not degrade the linear stacked sandwich configurations compared with the pristine hydrocarbon ligand complexes. Different from the N-doped complexes, the Bdoped ligands lead to more charge transfers from metal atoms, and such behavior allows for the enhanced structure stabilities and adds the advantage of electronic and magnetic properties manipulation. Moreover, the B-doped ligand makes the one-dimensional sandwich molecular wires conserve half metallic properties of the pristine molecular wires, undergo half metal−semiconductor transition, and vice versa. Thus, a novel strategy for efficient tailoring of the electronic and magnetic properties of metal−ligand sandwich complexes is presented.

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

Cited by 12 publications

References 21 publications

Study on Electronic Properties of Composite Clusters toward Nanoscale Functional Advanced Materials

Study on Electronic Properties of Composite Clusters toward Nanoscale Functional Advanced Materials

Investigation of the Electronic Structures of Organolanthanide Sandwich Complex Anions by Photoelectron Spectroscopy: 4f Orbital Contribution in the Metal–Ligand Interaction

Tunable Electronic and Magnetic Properties of Boron/Nitrogen-Doped BzTMCpTMBz/CpTMCpTMCp Clusters and One-Dimensional Infinite Molecular Wires

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

Cited by 12 publications

References 21 publications

Study on Electronic Properties of Composite Clusters toward Nanoscale Functional Advanced Materials

Study on Electronic Properties of Composite Clusters toward Nanoscale Functional Advanced Materials

Investigation of the Electronic Structures of Organolanthanide Sandwich Complex Anions by Photoelectron Spectroscopy: 4f Orbital Contribution in the Metal–Ligand Interaction

Tunable Electronic and Magnetic Properties of Boron/Nitrogen-Doped BzTMCp*TMBz/CpTMCp*TMCp Clusters and One-Dimensional Infinite Molecular Wires

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Tunable Electronic and Magnetic Properties of Boron/Nitrogen-Doped BzTMCpTMBz/CpTMCpTMCp Clusters and One-Dimensional Infinite Molecular Wires