Unexpected XPS Binding Energy Observations Further Highlighted by DFT Calculations of Ruthenocene-Containing [IrIII(ppy)2(RCOCHCORc)] Complexes: Cytotoxicity and Crystal Structure of [Ir(ppy)2(FcCOCHCORc)]

The series of iridium(III) complexes, [Ir(ppy)₂(RCOCHCOR')], with R = CH₃ and R' = CH₃ (<b>1</b>), Rc (<b>2</b>), and Fc (<b>3</b>), as well as R = Rc and R' = Rc (<b>4</b>) or Fc (<b>5</b>), and R = R' = Fc (<b>6</b>), ppy = 2-phenylpyridinyl, Fc = Fe^II(η⁵-C₅H₄)(η⁵-C₅H₅), and Rc = Ru^II(η⁵-C₅H₄)(η⁵-C₅H₅), has been investigated by single-crystal X-ray crystallography and X-ray photoelectron spectroscopy (XPS) supplemented by DFT calculations. Here, in the range of 3.74 ≤ Σχ_R ≤ 4.68, for Ir 4f, Ru 3d and 3p and N 1s orbitals, binding energies unexpectedly decreased with increasing Σχ_R (Σχ_R = the sum of Gordy group electronegativities of the R groups on β-diketonato ligands = a measure of electron density on atoms), while in Fe 2p orbitals, XPS binding energy, as expected, increased with increasing Σχ_R. Which trend direction prevails is a function of main quantum level, n = 1, 2, 3…, sub-quantum level (s, p, d, and f), initial state energies, and final state relaxation energies, and it may differ from compound series to compound series. Relations between DFT-calculated orbital energies and Σχ_R followed opposite trend directions than binding energy/Σχ_R trends. X-ray-induced decomposition of compounds was observed. The results confirmed good communication between molecular fragments. Lower binding energies of both the Ir 4f_7/2 and N 1s photoelectron lines are associated with shorter Ir-N bond lengths. Cytotoxic tests showed that <b>1</b> (IC₅₀ = 25.1 μM) and <b>3</b> (IC₅₀ = 37.8 μM) are less cytotoxic against HeLa cells than cisplatin (IC₅₀ = 1.1 μM), but more cytotoxic than the free β-diketone FcCOCH₂COCH₃ (IC₅₀ = 66.6 μM).