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Photodetachment Dynamics and Structural Flexibility of Undercoordinated Iridium Halides IrCln− (n = 3−5): An Experimental and Theoretical Investigation

Journal Article · · ChemPhysChem
 [1];  [2];  [1];  [1];  [1];  [1];  [3];  [4];  [1]
  1. East China Normal Univ. (ECNU), Shanghai (China)
  2. Donghua Univ., Shanghai (China)
  3. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
  4. East China Normal Univ. (ECNU), Shanghai (China); Shanxi Univ., Taiyuan (China)
+ Show Author Affiliations
Three undercoordinated iridium chloride anions, IrCln− (n = 3–5), and their neutral counterparts were investigated by cryogenic anion photoelectron spectroscopy and theoretical calculations. Photodetachment of IrCln− leads to the formation of the corresponding neutral complex, i.e., a triplet ground state for n = 3, a quartet for n = 4, and close-lying singlet and triplet for n = 5. The vertical detachment energies are determined to be 3.89, 4.98, and 5.14 eV for n = 3, 4, and 5, respectively, revealing superhalogen anion properties with increasing electron detachment energies as chloride ligands added. The IrCl3− spectrum features an extremely broad, lowest electron binding energy band, attributed to resonant autodetachment with prominent non-Franck–Condon profiles. In IrCl5−, detachment prompts a d-orbital rearrangement that drives a structural transformation from a twisted square-based pyramidal to a trigonal–bipyramidal geometry in the singlet state. In conclusion, these findings provide insights into the electronic and structural adaptability of iridium halides, advancing our understanding of ligand exchange reactions and dissociative stability in transition metal complexes.
Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
3007289
Report Number(s):
PNNL-SA--211617
Journal Information:
ChemPhysChem, Journal Name: ChemPhysChem Journal Issue: 15 Vol. 26; ISSN 1439-4235; ISSN 1439-7641
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English

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