Crystal structure, optical properties, spectroscopic characterization and density functional theory studies of a new rhodium (i)-imidazolidin-2-ylidene complexes: Synthesis, characterization and cytotoxic properties

Rhodium(I) complexes bearing imidazolidin-2-ylidene ligands have been widely used in catalytic chemistry, but there are very few reports of the biological properties of these type complexes. A series of [RhCl(COD)(NHC)] complexes were synthesized. The structures of all compounds were characterized by 1H NMR, 13C NMR, IR and elemental analysis techniques, which supported the proposed structures. The single-crystal structures of complexes 1a and 1c have been determined. Single-crystal X-ray diffraction analysis indicates that complexes 1a and 1c crystallize in the centrosymmetric space groups P n m a and I 1 2/a 1 of the orthorhombic and monoclinic systems respectively. The ground state geometry of these complexes was optimized using density functional theory (DFT) at mixed double zeta basis set, 6-31G(d) for H, C, N, O and Cl and LANL2DZ for Rh. The presence of the different functional groups and the nature of their vibrations were identified by the experimental and theoretical infrared spectra. The optical properties of the studied complex were determined experimentally using UV-visible and photoluminescence techniques in solid-state and theoretically using the TD-DFT method. Hirshfeld surface analysis employing 3D molecular surface contours and 2D fingerprint plots has been used to analyze intermolecular interactions present in the solid-state. The cytotoxic properties of the rhodium(I)-NHC complexes have been assessed in various human cancer lines, including cisplatin-sensitive and resistant cells. IC50 values of these four complexes were determined by the MTS-based assay on three human cancer cell lines; brain (SH-SY5Y), colon (HTC116), and liver (Hep 3B). Substances 1a-d showed 100% anticarcinogenic effect in cancer cell lines at 50 and 100 mu M.