Critical Role of CF3 Groups in the Electronic Stabilization of [PdAu24(C≡CC6H3(CF3)2)18]2– as Revealed by Gas-Phase Anion Photoelectron Spectroscopy
Open Access
- 21 October 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry Letters
- Vol. 12 (42), 10417-10421
- https://doi.org/10.1021/acs.jpclett.1c02906
Abstract
The role of alkynyl ligands with electron-withdrawing nature in the stability of metal clusters was investigated by gas-phase anion photoelectron spectroscopy (PES) on heteroleptic cluster anions [PdAu24(C≡CArF)18–x(C≡CPh)x]2– (ArF = 3,5-(CF3)2C6H3). Gas-phase PES on the cluster anions with specific x (= 0–6) revealed that electron binding energies decreased linearly with x, indicating that the electron-withdrawing CF3 substituents on the alkynyl ligand played a critical role in the electronic stabilization of [PdAu24(C≡CArF)18]2–. Density functional theory calculations reproduced the decrease of electron binding energies and rationally explained the ligand effect by a mechanism similar to the modulation of the work function of gold films by organic monolayers.This publication has 43 references indexed in Scilit:
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