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Here we explore the effect of the nature of organic ligands in rhenium cluster complexes [Re6Q8L6]4− (where Q=S or Se, and L=benzotriazole, 1,2,3‐triazole or 1,2,4‐triazole) on the biological properties of the complexes, in particular on the cellular toxicity, cellular internalization and localization. Specifically, the study describes the synthesis and detailed characterization of the structure, luminescence and electrochemical properties of the four new Re6 clusters with 1,2,3‐ and 1,2,4‐triazoles. Biological assays of these complexes are also discussed in addition to those with benzotriazole using cervical cancer (HeLa) and immortalized human fibroblasts (CRL‐4025) as model cell lines. Our study demonstrates that the presence of hydrophobic and π‐bonding rich units such as the benzene ring in benzotriazole significantly enhances cellular internalization of rhenium clusters. These ligands facilitate binding of the clusters to DNA, which results in increased cytotoxicity of the complexes. [ABSTRACT FROM AUTHOR]

The potential of 2‐(alkylsulfanyl)azine ligands for crystal engineering of functional Ag(I) complexes has been firstly demonstrated. The reaction of AgNO3, AgClO4 and AgOTf with 2‐(alkylsulfanyl)pyridines, ‐pyrimidines, and ‐quinolines gives a series of new Ag(I) compounds that range from mono‐ and dinuclear complexes to chain (1D), layered (2D) and framework (3D) coordination polymers (CPs). 2‐(Alkylsulfanyl)pyridines and ‐pyrimidines, depending on the reaction conditions, are assembled either into molecular complexes or CPs, while 2‐(alkylsulfanyl)quinolines afford dinuclear complexes exclusively. The most of compounds engineered feature site‐specific interactions such as Ag···Ag, Ag···O, and Ag···S ones. The 2‐(methylsulfanyl)quinoline (2‐MeSQn) complex, [Ag2(2‐MeSQn)2(NO3)2], displays room temperature intraligand (IL) phosphorescence, while the 2‐(methylsulfanyl)pyridine‐derived CPs emit dual luminescence expressed by IL fluorescence and phosphorescence. Moreover, cytotoxic activity of the compounds synthesized has been evaluated against hTERT lung fibroblasts, HeLa, MCF7, HepG2 and A549 cancer cells. [ABSTRACT FROM AUTHOR]