Triple 1D1D superatomic bonding. Au22(dppo)6 as a Π4- and Δ2-triply bonded cluster based on Au11 assembled units

Literature Information

Publication Date 2019-12-13
DOI 10.1039/C9CP05790K
Impact Factor 3.676
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Abstract

δ-Bonds have been intimately related to metal–metal bonds of d-elements since the archetypal d4–d4 [Re2Cl8]2− ion with a σ2π4δ2 bond. Currently, the notion of multiple superatom arrangements as initial steps toward molecular materials within the building-up approach is dominated by P-shell characteristics, as given in the well-described Au25(SR)18 ligand protected cluster. In this work we rationalize the Au22(dppo)6 cluster as a triple-bonded 22-valence electron (ve) supermolecule, featuring a bonding scheme based on 1D + 1D shell combinations, which largely contrasts with the 14-ve Au38(SR)24 with mainly 1P + 1P patterns mimicking a F2 molecule. The resulting Π4Δ2-bonding pattern shows an unprecedented superatomic counterpart of a d-shell based bond inherently related to transition-metal dimers, adding useful key aspects to the understanding of species based on cluster-assembly.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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