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Chem Asian J. 2017 Jan 3;12(1):145-158. doi: 10.1002/asia.201601414. Epub 2016 Dec 13.

Palladium(II) Acetylide Complexes with Pincer-Type Ligands: Photophysical Properties, Intermolecular Interactions, and Photo-cytotoxicity.

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State Key Laboratory of Synthetic Chemistry, Institute of Molecular Functional Materials, Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong SAR, China.
School of Chemistry and Chemical Engineering, Hainan Normal University, Haikou, 571158, China.
HKU Shenzhen Institute of Research and Innovation, Shenzhen, Guangdong, 518053, China.


Two classes of cationic palladium(II) acetylide complexes containing pincer-type ligands, 2,2':6',2''-terpyridine (terpy) and 2,6-bis(1-butylimidazol-2-ylidenyl)pyridine (C^N^C), were prepared and structurally characterized. Replacing terpy with the strongly σ-donating C^N^C ligand with two N-heterocyclic carbene (NHC) units results in the PdII acetylide complexes displaying phosphorescence at room temperature and stronger intermolecular interactions in the solid state. X-ray crystal structures of [Pd(terpy)(C≡CPh)]PF6 (1) and [Pd(C^N^C)(C≡CPh)]PF6 (7) reveal that the complex cations are arranged in a one-dimensional stacking structure with pair-like PdII ⋅⋅⋅PdII contacts of 3.349 Å for 1 and 3.292 Å for 7. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were used to examine the electronic properties. Comparative studies of the [Pt(L)(C≡CPh)]+ analogs by 1 H NMR spectroscopy shed insight on the intermolecular interactions of these PdII acetylide complexes. The strong Pd-Ccarbene bonds render 7 and its derivative sufficiently stable for investigation of photo-cytotoxicity under cellular conditions.


intermolecular interactions; palladium; phosphorescence; photo-cytotoxicity

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