The rational design of the ligands around transition metals has achieved success in the development of anticancer complexes. In this contribution, a series of organometallic half-sandwich iridium(iii) complexes with various corresponding counteranions have been prepared and characterized. The size and coordination ability of the counteranions exert a great influence on the chemical reactivity and anticancer activity of these complexes. The influence of the counteranions on the cell cycle, apoptosis, ROS and mitochondrial membrane potential is also discussed. This work has shown for the first time that the modification of counteranions can affect the anticancer activity of transition metal-based complexes.

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Six topologically diverse complexes based on the Ag(I)/2-sulfobenzoate/N-donor ligands system [Ag 2 (sb)] n (1), [Ag 4 (sb) 2 (apy) 4 ] (2), [Ag 2 (sb) 2 (apysulfobenzoate dianion, apy=2-aminopyridine, bipy=4,4 0 -bipyridine, bpe=1,2bis(4-pyridyl)ethylene, and hmt= hexamethylenetetramine) were synthesized and characterized. Complex 1, a water-soluble species, is a two-dimensional (2-D) structure constructed by [Ag 2 (sb)] binuclear units. Complexes 2 and 3 are tetrameric and dimeric species, respectively. For both complexes 2 and 3 hydrogen bonds generate one-dimensional (1-D) chains, and weak interactions such as Ag 3 3 3 π or C-H 3 3 3 π extend chains into three-dimensional (3-D) supramolecular structures. Complex 4 is a 1-D polymer with double ladder chains connected by Ag 3 3 3 Ag bonds. Complex 5 is a 2-D brick-wall-like layer framework. Complex 6 is a 2-D polymer. Moreover, complexes 4-6 are assembled into 3-D supramolecular frameworks by hydrogen bonds, π-π and C-H 3 3 3 π interactions. Additionally, Ag 3 3 3 Ag, Ag 3 3 3 π, and N-H 3 3 3 Ag interactions are found in these complexes. These interactions provide important roles in the assembly of the structures and function properties. And in particular the influences of Ag 3 3 3 Ag, Ag 3 3 3 π, and π-π interactions on the conducting properties are discussed. In all, thermal stability behaviors, fluorescent properties, and electric conductivities provide a way of understanding the relationship between these diverse structures and properties.

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Three 2,5-tpa complexes [AgIJPPh 3 ) 2 (2,5-tpa)] n (1), [Ag 2 (2,5-tpa)(2-apy) 2 ] n (2) and [{Ag 2 (2,5-tpa)(hmt) 2 } •3H 2 O] n (3) have been obtained and characterized by single-crystal X-ray analyses, elemental analyses, IR spectroscopy, and TG and proton-conductivity analyses, where 2,5-tpa stands for thiophene-2,5dicarboxylic dianions, PPh 3 is triphenyl phosphine, 2-apy is 2-aminopyridine and hmt is hexamethylenetetramine. The structures of 1-3 adopt 1D to 3D frameworks. Complex 1 is a one-dimensional sandwich-like polymer containing a 1D semi-symmetric ham backbone made up of [Ag(2,5-tpa)] units and PPh 3 "bread layers". In complex 2, the 2,5-tpa ligands bridge Ag atoms to form a 2D fishbone-shaped layer with weak π⋯π interactions and intra-molecular N-H⋯O hydrogen bonds. In 3, the 2,5-tpa ligands bridge two Aghmt layers to form a 3D wavy structure. Topological analyses were performed and the results are a 5-c nov net, a 3,4-c {6•10 2 }{6 2 •10 4 } net and a 3,4,6-c {4 4The structural diversity of the complexes results from the different neutral ligands in the structures, which has an important impact on the proton conductivities of the complexes. The complexes exhibited superprotonic conductivities of 1.99 × 10 −2 S cm −1 for 1, 4.25 × 10 −3 S cm −1 for 2 and 1.98 × 10 −3 S cm −1 for 3 at room temperature in a KNO 3 -K 4 Fe(CN) 6 -K 3 Fe(CN) 6 electrolyte. The proton conductivities of polymer films from 1 and 2 with PVDF (polyvinylidene fluoride) are 2.17 × 10 −3 S cm −1 and 8.99 × 10 −4 S cm −1 , respectively.

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