Heterobimetallic Pt II -Au I Complexes Comprising Unsymmetrical 1,1-Bis(diphenylphosphanyl)methane Bridges: Synthesis, Photophysical, and Cytotoxic Studies

Hamid R. Shahsavari*, Nora Giménez, Elena Lalinde, M. Teresa Moreno, Masood Fereidoonnezhad, Reza Babadi Aghakhanpour, Mehri Khatami, Foroogh Kalantari, Zahra Jamshidi, Mozhdeh Mohammadpour

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

In the present work, a series of aryl-cycloplatinated(II) complexes with general formula [Pt(C ^ N)(Ar)(κ 1 -dppm)], 1, [C ^ N = 7,8-benzoquinolinyl (bzq) or 2-phenylpyridinyl (ppy); Ar = C 6 F 5 or p-MeC 6 H 4 , dppm = 1,1-bis(diphenylphosphanyl)methane] was employed in the reaction with AuCl(SMe 2 ) in order to generate heterobimetallic Pt II -Au I complexes, [Pt(C ^ N)(Ar)(µ-dppm)Au(Cl)], 2, featuring a dppm bridge between the metal centers. The expectation was to induce metallophilic character into the excited state and to reduce non-radiative deactivation pathways of the dangling auxiliary κ 1 -dppm ligand through molecular motions, to improve the photophysical properties. After characterization of the new complexes by means of NMR spectroscopy and X-ray crystallography technique, the photophysical properties of all the complexes were investigated by UV/Vis and photoluminescence spectroscopy. Both of the monometallic complexes and heterobimetallic products have shown to be luminescent in different states and temperature conditions. However, by addition of Au I , the impact on the photophysics of the heterobimetallic products in relation to the precursors with dangling dppm is minimal, a finding which can be attributed to the absence of a Pt II -Au I bond in these compounds. Indeed, the character of the excited states of the monomer Pt II complexes and their corresponding bimetallic Pt II -Au I ones are similar, as confirmed by density functional theory (DFT) and time resolved DFT (TD-DFT) calculations. The cytotoxic activities of the compounds along with that of [ClAu(µ-dppm)AuCl] were evaluated against human breast cancer (MCF-7), human lung cancer (A549), human ovarian cancer (SKOV3) and non-tumorigenic epithelial breast (MCF-10A) cell lines. The highest activity was found for the heterometallic Pt-Au species, suggesting a cooperative effect of both metallic fragments. The most cytotoxic compound, i.e. [Pt(bzq)(p-MeC 6 H 4 )(µ-dppm)Au(Cl)], 2b, effectively causes cell death in MCF-7 cancer cell line by inducing apoptosis. Fluorescence microscopy experiments for 2a were performed.

Original languageEnglish
Pages (from-to)1360-1373
Number of pages14
JournalEuropean Journal of Inorganic Chemistry
Volume2019
Issue number10
DOIs
Publication statusPublished - 14 Mar 2019
Externally publishedYes

Keywords

  • Cytotoxicity
  • Gold
  • Heterobimetallic complexes
  • P ligands
  • Photophysics
  • Platinum

Fingerprint Dive into the research topics of 'Heterobimetallic Pt <sup>II</sup> -Au <sup>I</sup> Complexes Comprising Unsymmetrical 1,1-Bis(diphenylphosphanyl)methane Bridges: Synthesis, Photophysical, and Cytotoxic Studies'. Together they form a unique fingerprint.

Cite this