Cyclic ion mobility of doped [MAu24L18]2- superatoms and their fragments (M = Ni, Pd and Pt; L = alkynyl)

Frank Hennrich; Shun Ito; Patrick Weis; Marco Neumaier; Shinjiro Takano; Tatsuya Tsukuda; Manfred M Kappes

doi:10.1039/d3cp06192b

Cyclic ion mobility of doped [MAu₂₄L₁₈]^2- superatoms and their fragments (M = Ni, Pd and Pt; L = alkynyl)

Phys Chem Chem Phys. 2024 Mar 6;26(10):8408-8418. doi: 10.1039/d3cp06192b.

Authors

Frank Hennrich^{1

2}, Shun Ito³, Patrick Weis¹, Marco Neumaier^{1

4}, Shinjiro Takano³, Tatsuya Tsukuda³, Manfred M Kappes^{1

4

2}

Affiliations

¹ Institute of Physical Chemistry, Karlsruhe Institute of Technology, Fritz-Haber-Weg 2, Karlsruhe 76131, Germany. manfred.kappes@kit.edu.
² Institute of Quantum Materials and Technologies, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen 76344, Germany.
³ Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
⁴ Institute of Nanotechnology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen 76344, Germany.

PMID: 38407473
DOI: 10.1039/d3cp06192b

Abstract

Collision-induced dissociation and high-resolution cyclic ion mobility mass spectrometry, along with quantum chemical calculations and trajectory simulations, were used to compare the structures of isolated [MAu₂₄(CCR)₁₈]^2-, M = Ni, Pd, or Pt, and their associated fragment ions. The three different alkynyl ligand-stabilized (CCR, R = 3,5-(CF₃)₂C₆H₃), transition metal-doped, gold cluster dianions showed mutually resolvable collision cross sections (CCS), which were ordered consistently with their molecular structures from X-ray crystallography. All three [MAu₂₄(CCR)₁₈]^2- species fragment by sequential diyne loss to form [MAu₂₄(CCR)_18-n]^2-, with n up to 12. The resultant fragment isomer distributions are significantly n- and M-dependent, and hint at a process involving concerted elimination of adjacent ligands. In particular [NiAu₂₄(CCR)₁₈]^2- also fragments to generate alkyne-oligomers, an inference supported by the parallel observation of precursor dianion isomerization as collision energy is increased.