Novel Imino Thioether Complexes of Platinum(II): Synthesis, Structural Investigation, and Biological Activity

The reactions of the nitrile complexes <i>cis</i>- and <i>trans</i>-[PtCl₂(NCR)₂] (R = Me, Et, CH₂Ph, Ph) with an excess of ethanethiol, EtSH, in the presence of a catalytic amount of <i>n</i>-BuLi in tetrahydrofuran (THF), afforded in good yield the bis-imino thioether derivatives <i>cis</i>-[PtCl₂{<i>E</i>-N­(H)C­(SEt)­R}₂] (R = Me (<b>1</b>), Et (<b>2</b>), CH₂Ph (<b>3</b>), Ph (<b>4</b>)) and <i>trans</i>-[PtCl₂{<i>E</i>-N­(H)C­(SEt)­R}₂] (R = Me (<b>5</b>), Et (<b>6</b>), CH₂Ph (<b>7</b>), Ph (<b>8</b>)). The imino thioether ligands assumed the <i>E</i> configuration corresponding to a <i>cis</i> addition of the thiol to the nitrile triple bond. The spectroscopic properties of these complexes have been reported along with the molecular structures of <b>1</b>, <b>2</b>, and <b>7</b> as established by X-ray crystallography which indicated that these compounds exhibit square-planar coordination geometry around the platinum center. Four N–H···Cl intermolecular contacts (N–H···Cl ca. 2.5–2.7 Å) between each chlorine atom and the N–H proton of the imino thioether ligand gave rise to “dimers” Pt₂Cl₄L₄ (L = imino thioether) formed by two PtCl₂L₂ units. The cytotoxic properties of these new platinum­(II) complexes were evaluated against various human cancer cell lines. Among all derivatives, <i>trans</i>-[PtCl₂{<i>E</i>-N­(H)C­(SEt)­CH₂Ph}₂] showed the greatest in vitro cytotoxic activity being able to decrease cancer cell viability roughly 3-fold more effectively than cisplatin

Interplay between Structural and Dielectric Features of New Low k Hybrid Organic–Organometallic Supramolecular Ribbons

The synthesis and characterization of low k one-dimensional (1D) hybrid organic–organometallic supramolecular ribbons <b>3a</b>,<b>b</b>, through halogen-bond driven co-crystallization of <i>trans</i>-[Pt­(PCy₃)₂(CC-4-py)₂] (<b>1</b>) with 1,4-diiodotetrafluorobenzene (<b>2a</b>) and <i>trans</i>-1,2-bis-(2,3,5,6-tetrafluoro-4-iodophenyl)-ethylene (<b>2b</b>), are reported. The co-crystals <b>3a</b>,<b>b</b> have been obtained by isothermal evaporation of a chloroform solution containing the corresponding starting materials at room temperature. X-ray structure determinations show that noncovalent interactions other than halogen bonds help in the construction of the crystal packing; these interactions are stronger in <b>3b</b>, thus reducing the chain mobility with respect to <b>3a</b>. Accordingly, the broadband dielectric spectroscopic determinations, carried out from 10^–2 to 10⁷ Hz and at a temperature ranging from 25 to 155 °C, showed that both <b>3a</b> and <b>3b</b> materials exhibit a real component of dielectric permittivity (ε′) significantly lower than SiO₂. In particular in the case of <b>3b</b>, the rigidity of the 1D chain explains the observed ε″ and tan δ values. A permittivity value that is significantly lower than that of the silica reference, tan δ values lower than 0.02 in the entire investigated temperature range, and less than 0.004 at <i>T</i> < 100 °C make <b>3b</b> a very promising low k hybrid organic–organometallic material for application as dielectric films in next generation microelectronics