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Cluster Chemistry: Metal Clusters of the Main Group and Transition Elements

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: closed (31 August 2021) | Viewed by 4041

Special Issue Editors


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Guest Editor
Chemistry Department, University Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany
Interests: cryochemistry; solution chemistry of metastable group 14 monohalides; metalloid clusters of group 14 and group 11 elements; group 14 nanoparticles; single crystal x-ray structure analysis; cluster chemistry

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Guest Editor
Institute for Chemistry, Solid State Chemistry Group, University of Rostock, Albert-Einstein-Str. 3a, 18057 Rostock, Germany
Interests: transition metal-cluster; inorganic synthesis; X-ray structure; ionic liquids; tetracyanoborates; materials properties

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Guest Editor
School of Materials Science and Engineering, Nankai University, Tianjin 300350, China
Interests: zintl anion; cluster chemistry; metal-metal bond; maingroup metals; coordination chemistry

Special Issue Information

Dear Colleagues,

In the last few decades, nanotechnology has increasingly become a molecular regime, leading to a growing interest in main group and transition metal cluster compounds as molecular models for metal nanoparticles. Many results are obtained within the field of precious transition metals due to easily available starting compounds and synthetic procedures, like the Brust–Schiffrin method. However, in recent years, synthetic routes to new cluster compounds have been successfully established as well. This has led to remarkable results in the field of cluster chemistry of metals, opening our eyes to the complexity within the nanoscaled molecular regime. In recent years, investigations have started to spread out to define the extraordinary material properties of such compounds, such as luminescence, X-ray absorption properties, singlet oxygen production, surface modification, nanostructuration, organics/inorganics hybrid composites, or functional surfaces, to name a few. Additionally, novel physical and chemical properties have been obtained for these cluster compounds that might be used in material science or for biological or (photo)catalytic applications.

This Special Issue aims to attract contributions from cluster chemistry from all metals and semimetals to further promote investigations on synthesis, structure, property, and applications of this novel group of cluster compounds, closing and/or bridging the gap to investigations in nanotechnology.

Prof. Dr. Andreas Schnepf
Prof. Dr. Martin Köckerling
Prof. Dr. Zhong-Ming Sun
Guest Editors

Manuscript Submission Information

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Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Metalcluster
  • Metalloid clusters
  • Nanoclusters
  • Polyhedral clusters
  • Transition metal cluster
  • Main group metal cluster
  • Zintl compound
  • Bonding
  • Properties
  • Metal–metal bonding
  • Synthesis
  • Crystal structure

Published Papers (1 paper)

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Research

14 pages, 3336 KiB  
Article
Photoexcitation of Ge9 Clusters in THF: New Insights into the Ultrafast Relaxation Dynamics and the Influence of the Cation
by Nadine C. Michenfelder, Christian Gienger, Melina Dilanas, Andreas Schnepf and Andreas-Neil Unterreiner
Molecules 2020, 25(11), 2639; https://doi.org/10.3390/molecules25112639 - 05 Jun 2020
Cited by 5 | Viewed by 3001
Abstract
We present a comprehensive femtosecond (fs) transient absorption study of the [Ge9(Hyp)3] (Hyp = Si(SiMe3)3) cluster solvated in tetrahydrofuran (THF) with special emphasis on intra- and intermolecular charge transfer mechanisms which can be tuned [...] Read more.
We present a comprehensive femtosecond (fs) transient absorption study of the [Ge9(Hyp)3] (Hyp = Si(SiMe3)3) cluster solvated in tetrahydrofuran (THF) with special emphasis on intra- and intermolecular charge transfer mechanisms which can be tuned by exchange of the counterion and by dimerization of the cluster. The examination of the visible and the near infrared (NIR) spectral range reveals four different processes of cluster dynamics after UV (267/258 nm) photoexcitation related to charge transfer to solvent and localized excited states in the cluster. The resulting transient absorption is mainly observed in the NIR region. In the UV-Vis range transient absorption of the (neutral) cluster core with similar dynamics can be observed. By transferring concepts of: (i) charge transfer to the solvent known from solvated Na in THF and (ii) charge transfer in bulk-like materials on metalloid cluster systems containing [Ge9(Hyp)3] moieties, we can nicely interpret the experimental findings for the different compounds. The first process occurs on a fs timescale and is attributed to localization of the excited electron in the quasi-conduction band/excited state which competes with a charge transfer to the solvent. The latter leads to an excess electron initially located in the vicinity of the parent cluster within the same solvent shell. In a second step, it can recombine with the cluster core with time constants in the picosecond (ps) timescale. Some electrons can escape the influence of the cluster leading to a solvated electron or after interaction with a cation to a contact pair both with lifetimes exceeding our experimentally accessible time window of 1 nanosecond (ns). An additional time constant on a tens of ps timescale is pronounced in the UV-Vis range which can be attributed to the recombination rate of the excited state or quasi conduction band of Ge9. In the dimer, the excess electron cannot escape the molecule due to strong trapping by the Zn cation that links the two cluster cores. Full article
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