Chapter 8
Electronic Properties of Transition
Metal-Benzene Sandwich Clusters
Tsugunosuke Masubuchi and Atsushi Nakajima
Abstract Organometallic clusters composed of transition metal atoms and benzene
molecules have been topics of great interest from both fundamental and technological points of view. In this chapter, we review the progress in the physical
chemistry of transition metal-benzene clusters. The intrinsic properties of transition
metal-benzene clusters as a function of cluster size are investigated by gasphase experiments, often in combination with quantum chemical calculations. In
particular, vanadium-benzene clusters denoted V n Bz m , showing magic numbers at
m = n + 1, n, and n – 1, are characterized to possess multiple-decker sandwich
structures, where vanadium atoms and benzene molecules are alternately piled up.
Moreover, the discovery of such multiple-decker formation is a cornerstone in
bottom-up approaches of molecular magnetism. The interplay of mass spectrometry,
laser spectroscopies, and density functional calculations reveals that multiple-decker
V n Bz m clusters exhibit monotonic increase in magnetic moment with the number of
layers. Anion photoelectron spectroscopic studies allow direct observations of the
geometric and electronic structures of sandwich clusters and their anions. Major
progress in this direction includes the recent characterization of tilted multipledecker sandwich cluster anions composed of manganese atoms and benzene
molecules. The sandwich clusters with high-spin characteristics will hopefully be
exploited as building blocks in advanced electronic and magnetic nanomaterials via
controlled assembly.
T. Masubuchi
Department of Chemistry, Faculty of Science and Technology, Keio University, Kohoku-ku,
Yokohama, Japan
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, Dalian, China
A. Nakajima ()
Department of Chemistry, Faculty of Science and Technology, Keio University, Kohoku-ku,
Yokohama, Japan
Keio Institute of Pure and Applied Sciences (KiPAS), Keio University, Kohoku-ku, Yokohama,
Japan
e-mail: nakajima@chem.keio.ac.jp
© Springer Nature Singapore Pte Ltd. 2020
T. Onishi (ed.), Theoretical Chemistry for Advanced Nanomaterials,
https://doi.org/10.1007/978-981-15-0006-0_8
313
Electronic Properties of Transition
Metal-Benzene Sandwich Clusters
Tsugunosuke Masubuchi and Atsushi Nakajima
Abstract Organometallic clusters composed of transition metal atoms and benzene
molecules have been topics of great interest from both fundamental and technological points of view. In this chapter, we review the progress in the physical
chemistry of transition metal-benzene clusters. The intrinsic properties of transition
metal-benzene clusters as a function of cluster size are investigated by gasphase experiments, often in combination with quantum chemical calculations. In
particular, vanadium-benzene clusters denoted V n Bz m , showing magic numbers at
m = n + 1, n, and n – 1, are characterized to possess multiple-decker sandwich
structures, where vanadium atoms and benzene molecules are alternately piled up.
Moreover, the discovery of such multiple-decker formation is a cornerstone in
bottom-up approaches of molecular magnetism. The interplay of mass spectrometry,
laser spectroscopies, and density functional calculations reveals that multiple-decker
V n Bz m clusters exhibit monotonic increase in magnetic moment with the number of
layers. Anion photoelectron spectroscopic studies allow direct observations of the
geometric and electronic structures of sandwich clusters and their anions. Major
progress in this direction includes the recent characterization of tilted multipledecker sandwich cluster anions composed of manganese atoms and benzene
molecules. The sandwich clusters with high-spin characteristics will hopefully be
exploited as building blocks in advanced electronic and magnetic nanomaterials via
controlled assembly.
T. Masubuchi
Department of Chemistry, Faculty of Science and Technology, Keio University, Kohoku-ku,
Yokohama, Japan
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, Dalian, China
A. Nakajima ()
Department of Chemistry, Faculty of Science and Technology, Keio University, Kohoku-ku,
Yokohama, Japan
Keio Institute of Pure and Applied Sciences (KiPAS), Keio University, Kohoku-ku, Yokohama,
Japan
e-mail: nakajima@chem.keio.ac.jp
© Springer Nature Singapore Pte Ltd. 2020
T. Onishi (ed.), Theoretical Chemistry for Advanced Nanomaterials,
https://doi.org/10.1007/978-981-15-0006-0_8
313