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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.

Author information

1
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.
2
School of Chemistry and Chemical Engineering, Hainan Normal University, Haikou, 571158, China.
3
HKU Shenzhen Institute of Research and Innovation, Shenzhen, Guangdong, 518053, China.

Abstract

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.

KEYWORDS:

intermolecular interactions; palladium; phosphorescence; photo-cytotoxicity

PMID:
27797451
DOI:
10.1002/asia.201601414
[Indexed for MEDLINE]

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