Platinum-based anticancer drugs are most likely the most successful group of bioinorganic compounds. Their apparent disadvantages have led to the development of anticancer compounds of other noble metals, resulting in several ruthenium-based drugs which have entered clinical trials on oncological patients. Besides ruthenium, numerous rhodium complexes have been recently reported as highly potent antiproliferative agents against various human cancer cells, making them potential alternatives to Pt- and Ru-based metallodrugs. In this review, half-sandwich Rh(III) complexes are overviewed. Many representatives show higher in vitro potency than and different mechanisms of action (MoA) from the conventional anticancer metallodrugs (cisplatin in most cases) or clinically studied Ru drug candidates. Furthermore, some of the reviewed Rh(III) arenyl complexes are also anticancer in vivo. Pioneer anticancer organorhodium compounds as well as the recent advances in the field are discussed properly, and adequate attention is paid to their anticancer activity, solution behaviour and various processes connected with their MoA. In summary, this work summarizes the types of compounds and the most important biological results obtained in the field of anticancer half-sandwich Rh complexes.

The extent of interactions with various biomolecules is a crucial feature of newly developed metallodrugs, worthy of thorough investigation, as its understanding helps uncover the fate of these xenobiotics in...

Studying the properties of complex molecules on surfaces is still mostly an unexplored research area because the deposition of the metal complexes has many pitfalls. Herein, we probed the possibility to produce surface hybrids by depositing a Co(II)-based complex with chalcone ligands on chemical vapor deposition (CVD)-grown graphene by a wet-chemistry approach and by thermal sublimation under high vacuum. Samples were characterized by high-frequency electron spin resonance (HF-ESR), XPS, Raman spectroscopy, atomic force microscopy (AFM), and optical microscopy, supported with density functional theory (DFT) and complete active space self-consistent field (CASSCF)/N-electron valence second-order perturbation theory (NEVPT2) calculations. This compound’s rationale is its structure, with several aromatic rings for weak binding and possible favorable π–π stacking onto graphene. In contrast to expectations, we observed the formation of nanodroplets on graphene for a drop-cast sample and microcrystallites localized at grain boundaries and defects after thermal sublimation.

The synthesis and properties of new chalcone ligand 4I-L ((2E)-1-[4-(1H-imidazol-1-yl)phenyl]-3-(4-iodophenyl)prop-2-en-1-one) and tetracoordinate Co(II) complex [Co(4I-L)2Cl2], (1a), are reported in this article. Upon recrystallization of 1a, the single crystals of [Co(4I-L)4Cl2]·2DMF·3Et2O (1b) were obtained and crystal structure was determined using X-ray diffraction. The non-covalent interactions in 1b were thoroughly analyzed and special attention was dedicated to interactions formed by the peripheral iodine substituents. The density functional theory (DFT), atoms in molecule (AIM) and noncovalent interaction (NCI) methods and electronic localization function (ELF) calculations were used to investigate halogen bond formed between the iodine functional groups and co-crystallized molecules of diethyl ether.

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Complexes [Ru(η6-pcym)(bpydca)Cl]PF6 (Rudca) and [Ir(η5-Cp*)(bpydca)Cl]PF6 (Irdca) were developed as model compounds for the investigation of multi-targeted ester-functionalized half-sandwich ruthenium(II) and iridium(III) complexes; pcym = 1-methyl-4-(propan-2-yl)benzene (p-cymene), bpydca = 2,2'-bipyridine-4,4'-diyldimethanediyl bis(dichloroacetate),...

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In the presence of carboxypeptidase, the hydrolytically stable complex [Os(η6-pcym)(L2)Cl]PF6 (2) partially released the bioactive substituent indomethacin, bound through the amide bond to the chelating 2-(1,3,4-thiadiazol-2-yl)pyridine-based moiety of L2. Stability...