Bifunctional Mononuclear Dysprosium Complexes: Single-Ion Magnet Behaviors and Antitumor Activities

Inorg Chem. 2019 Feb 18;58(4):2286-2298. doi: 10.1021/acs.inorgchem.8b02250. Epub 2019 Jan 30.

Abstract

Two mononuclear dysprosium complexes (Et3NH)[Dy(BrMQ)4]·H2O·DMF(BrMQ-Dy) and (Et3NH)[Dy(ClMQ)4]·H2O·DMF (ClMQ-Dy) (H-BrMQ = 5,7-dibromo-2-methyl-8-quinolinol, H-ClMQ = 5,7-dichloro-2-methyl-8-quinolinol) were synthesized and characterized. The Dy(III) ions in complexes BrMQ-Dy and ClMQ-Dy have a pseudo-D4d local symmetry. Magnetic characterizations reveal that complex BrMQ-Dy is a single-ion magnet and complex ClMQ-Dy exhibits field-induced slow magnetic relaxation behaviors. The calculated effective barriers of BrMQ-Dy, BrMQ-Dya, ClMQ-Dy, and ClMQ-Dya are 47.8, 27.3, 96.0, and 65.5 cm-1, respectively (BrMQ-Dya and ClMQ-Dya represent the desolvated samples of BrMQ-Dy and ClMQ-Dy, respectively). Ab initio calculations confirmed that coordination symmetry of the Dy(III) ions, electron-withdrawing ligands, and the guest molecules is a key factor affecting the magnetic dynamics of the two complexes. The IC50 values of BrMQ-Dy and ClMQ-Dy against BEL-7404, HeLa, and Hep-G2 cancer cells were 1.01-22.06 μM. Interestingly, two Dy(III) complexes were less toxic to normal HL-7702 cells. BrMQ-Dy and ClMQ-Dy significantly induced cell arrest at G2 phase and down-regulated the G2 phase-related protein levels. Various experiments suggested that BrMQ-Dy and ClMQ-Dy also caused dysfunction of mitochondrial pathways in HeLa cells. Taken together, the different in vitro anticancer activity of complexes BrMQ-Dy and ClMQ-Dy in the order of 5,7-dichloro substitution > 5,7-dibromo substitution.

MeSH terms

  • Antineoplastic Agents / chemistry*
  • Antineoplastic Agents / metabolism
  • Antineoplastic Agents / pharmacology*
  • Apoptosis / drug effects
  • Biological Transport
  • Coordination Complexes / chemistry*
  • Coordination Complexes / metabolism
  • Coordination Complexes / pharmacology*
  • Dysprosium / chemistry*
  • HeLa Cells
  • Humans
  • Magnetic Phenomena*
  • Membrane Potential, Mitochondrial / drug effects
  • Models, Molecular
  • Molecular Conformation

Substances

  • Antineoplastic Agents
  • Coordination Complexes
  • Dysprosium