Air-stable Palladium N-Heterocyclic Carbene based CCC-NHC Pincer Complexes: Synthesis, Characterization, Photophysical and Raman Vibrational Studies, and DFT Studies, Plus Observation of an Abnormal Carbene Pincer

Authors

Jason A. Denny, Mississippi State UniversityFollow
Georgette M. Lang, Mississippi State UniversityFollow
Shane Autry, University of Mississippi Main CampusFollow
Vivek Dixit, Mississippi State UniversityFollow
Tyler L. Woodby, Mississippi State UniversityFollow
Annie McClellan, University of Mississippi Main Campus
Jaclyn M. Trate, University of Mississippi Main Campus
Nathan I. Hammer, University of Mississippi Main CampusFollow
Charles Edwin Webster, Mississippi State UniversityFollow
Thedford K. Hollis, Mississippi State UniversityFollow

ORCID

Hollis: https://orcid.org/0000-0002-5470-9811

Abstract

A series of CCC-NHC pincer Pd(II)X complexes, where X = Cl, Br, or I, were synthesized by a metalation/transmetalation reaction sequence and characterized by NMR and Raman spectroscopy, photophysical studies, X-ray crystallography, and DFT computational studies. This is the first detailed report of the CCC-NHC pincer Pd complexes analogous the previously reported Pt analogs. Photophysical measurements show that by varying the X ligand, the emission wavelength can be tuned. The chloride complex is a water and air stable blue emitter with a quantum yield of 46% and all three complexes have photostabilities >90%. A combined DFT and TD-DFT study has been carried out to investigate ground state and excited state geometries as well as absorption and emission processes of CCC-NHC Pd complexes. Theoretical results were compared with the corresponding experimental results and showed good agreement. Raman spectroscopy (computational and experimental) was used to examine Pd-X vibrations which have been rarely reported in the literature. Several by-products of the metalation/transmetalation procedure were identified. A rare mixed normal/abnormal carbene pincer Pd(II)Cl complex was isolated and crystallographically characterized.

Comments

To read article, visit https://doi.org/10.1016/j.jorganchem.2024.123419. For original file, please contact the authors. Embargo lifts on October 18, 2026.

Publisher

Elsevier Ltd.

DOI

https://doi.org/10.1016/j.jorganchem.2024.123419

Publication Date

Fall 10-18-2024

Requires

Microsoft Word

College

College of Arts and Sciences

Department

Department of Chemistry

Disciplines

Chemistry | Computational Chemistry | Inorganic Chemistry | Organic Chemistry | Physical Chemistry

Recommended Citation

Jason A. Denny, Georgette M. Lang, Shane Autry, Vivek Dixit, Tyler L. Woodby, Annie McClellan, Jaclyn M. Trate, Nathan I. Hammer, Charles Edwin Webster, T. Keith Hollis, Air-stable Palladium N-Heterocyclic Carbene based CCC-NHC Pincer Complexes: Synthesis, Characterization, Photophysical and Raman Vibrational Studies, and DFT Studies, Plus Observation of an Abnormal Carbene Pincer, Journal of Organometallic Chemistry, 2024, 123419, https://doi.org/10.1016/j.jorganchem.2024.123419.