Arene Moiety Research Articles

How Do Positions of Phosphito Units on a Calix[4]Arene Platform Affect the Enantioselectivity of a Catalytic Reaction?

Three chiral diphosphites, (S,S)-5,17-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)-25,26,27,28-tetrapropyloxycalix[4]arene (1), (S,S)-5,11,17,23-tetra-tert-butyl-25,27-dipropoxy-26,28-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)calix[4]arene (2) and (S,S)-5,11,17,23-tetra-tert-butyl-25,26-dipropoxy-27,28-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)calix[4]arene (3), based on conical calix[4]arene were investigated in the rhodium-catalyzed asymmetric hydrogenation of α-dehydroamino esters. High conversions were observed after 24 h under 5 bar of hydrogen whatever the employed diphosphite, and the chiral induction increases in the order 1 < 3 < 2. This may be due to the presence of the calix[4]arene moiety, which by its presence modifies the second coordination sphere of the catalytic center. The larger steric hindrance around the rhodium atom leads to the higher enantiomeric excess.

Suppressing Water Uptake and Increasing Hydroxide Conductivity in Ring-Opened Polynorbornene Ion-Exchange Materials via Backbone Design

In this study, we aimed to decrease segmental mobility in ring-opened polynorbornene anion-exchange membranes (AEMs) as a strategy to suppress swelling. This was accomplished by copolymerization of a norbornene-anthracene cycloadduct with cationic tetraaminophosphonium norbornene monomers to afford AEMs with glass transition temperatures above 100 °C. The anthracenyl side groups appended to the poly(vinylene-1,3-cyclopentylene) chain resulted in lower water uptake for the phosphonium-functionalized AEM when compared to an analogue without the arene moiety. Though chemical aging of these AEMs was noted over time, the benefits of rigidifying the polymer backbone were clear. Additionally, we have noted that the choice of dialkylamino groups around the phosphorus center plays a key role in alkaline stability of these phosphonium-based AEMs.

A rapid construction of 4(3H)-quinazolinone and related ring under ultrasound irradiation: In silico/in vitro studies of compounds synthesized

Because of importance of the quinazolinone framework particularly in medicinal and pharmaceutical chemistry efforts have been devoted to establish convenient methods for the synthesis of quinazolinone derivatives. Due to our interest in this class of compounds as potential inhibitor chorismate mutase (MtbCM), a known target for the identification of anti-tubercular agents we report the rapid construction of 4(3H)-quinazolinone ring under ultrasound irradiation. The current sonochemical approach involved an iodine mediated reaction of 2-aminobenzamide or its derivatives with readily available alcohols in aqueous DMSO under ultrasound. A series of 4(3H)-quinazolinone derivatives were prepared where substituents like aryl or heteroaryl ring or an alkyl or styryl moiety can be present at the C-2 position of the product. The analogues of quinazolinone such as pteridin-4(3H)-one and pyrido[2,3-d]pyrimidin-4(3H)-one derivatives were also prepared using this sonochemical approach. Generally, a good yield of product was obtained when the C-2 substituent of the product was an arene moiety whereas the yield was acceptable to moderate in rest of the cases. The use of milder condition, inexpensive iodine as well as aqueous media and shorter duration seemed to be key features of this methodology. The in silico docking studies indicated 3d, 3n and 3u as possible inhibitors that showed H-bonding with the residues ASP69 and GLU106 and a common pi-alkyl interaction with the critical dimer interface residue ARG103 of MtbCM. When tested in vitro against MtbCM these compounds exhibited good activities (> 50% inhibition). The brief Structure-Activity-Relationship (SAR) study indicated beneficial effects of the C-2 substituent in the order benzene > pyridine > indole ring.

Metal Halide Exchange in Benzylborane NHC‐Adducts: The Effect of Backbone Alkylation in the N‐Heterocyclic Carbene

AbstractAmong other main group elements, the chemistry of boron has been stimulated by N‐heterocyclic carbenes (NHCs) as important ligands, the nature of which can significantly control the outcome of reactions. In four‐coordinate benzyl boranes of type (NHC)BH2CH2(o‐BrC6H4), we demonstrate this effect at the example of a lithiation silylation procedure. For NHC=IiPr lithiation of the arene ring by lithium‐bromide exchange with tBuLi ultimately leads to backbone substitution with proton rearrangement, as demonstrated by trapping with trimethylsilyl chloride. In contrast, such process is suppressed for NHC=IiPrMe, which undergoes lithiation and subsequent trimethyl‐silylation at the arene moiety.

Front Cover: Retro‐Friedel‐Crafts‐Type Acidic Ring‐Opening of Triptycenes: A New Synthetic Approach to Acenes (Chem. Eur. J. 12/2022)

The triptycene scaffold has been ring-opened by using an acidic retro-Friedel-Crafts-type reaction to give its corresponding anthrone product. 9-Hydroxytriptycenes and unsubstituted triptycene were ring-opened by treatment with TfOH. The electron-donating group on the arene moiety allows the reaction to proceed in the presence of weaker acids. Additionally, the reaction has been applied toward the synthesis of tetracene. More information can be found in the Research Article by T. Iwata, M. Shindo et al. (DOI: 10.1002/chem.202104160).

Retro-Friedel-Crafts-Type Acidic Ring-Opening of Triptycenes: A New Synthetic Approach to Acenes.

The triptycene scaffold has been ring-opened by using a retro-Friedel-Crafts-type reaction under acidic conditions to give its corresponding anthrone product. 9-Hydroxytriptycenes and unsubstituted triptycene undergo ring-opening reaction under strongly acidic conditions, such as with TfOH. An investigation of the substitution effect has revealed that the electron-donating group on the arene moiety allows the reaction to proceed in the presence of a weaker acid, such as TFA. In addition, the reaction has been successfully applied toward the synthesis of tetracene.

External-stimulus-triggered conformational inversion of mechanically self-locked pseudo[1]catenane and gemini-catenanes based on A1/A2-alkyne-azide-difunctionalized pillar[5]arenes.

Herein, we report a methodology for constructing mechanically self-locked molecules (MSMs) through the efficient intramolecular copper(i)-catalyzed alkyne–azide cycloaddition (CuAAC) of self-threaded A1/A2-azido-propargyl-difunctionalized pillar[5]arenes. The obtained monomeric “pseudo[1]catenane” and dimeric “gemini-catenane” were isolated and fully characterized using mass spectrometry, nuclear magnetic resonance (NMR) spectroscopy, and X-ray crystallography. Upon investigation by 1H NMR spectroscopy in chloroform, the observed motion for the threaded ring in the pseudo[1]catenane was reversibly controlled by the temperature, as demonstrated by variable-temperature 1H NMR studies. Two gemini-catenane stereoisomers were also isolated in which the two pillar[5]arene moieties threaded by two decyl chains were aligned in different topologies. Furthermore, the conformational inversion of pseudo[1]catenane and the gemini-catenanes triggered by solvents and guests was investigated and probed using 1H NMR spectroscopy, isothermal titration calorimetry, and single-crystal X-ray analysis.

Supramolecular nanocapsules as two-fold stabilizers of outer-cavity sub-nanometric Ru NPs and inner-cavity ultra-small Ru clusters.

The synthesis of metallic nanoparticles (MNP) with high surface area and controlled shape is of paramount importance to increase their catalytic performance. The detailed growing process of NP is mostly unknown and understanding the specific steps would pave the way for a rational synthesis of the desired MNP. Here we take advantage of the stabilization properties exerted by the tetragonal prismatic supramolecular nanocapsule 8·(BArF)8 to develop a synthetic methodology for sub-nanometric RuNP (0.6-0.7 nm). The catalytic properties of these sub-nanometric nanoparticles were tested on the hydrogenation of styrene, obtaining excellent selectivity for the hydrogenation of the alkene moiety. In addition, the encapsulation of [Ru5] clusters inside the nanocapsule is strikingly observed in most of the experimental conditions, as ascertained by HR-MS. Moreover, a thorough DFT study enlightens the nature of the [Ru5] clusters as tb-Ru5H2(η6-PhH)2(η6-pyz)3 (2) trapped by two arene moieties of the clip, or as tb-Ru5H2(η1-pyz)6(η6-pyz)3 (3) trapped between the two Zn-porphyrin units of the nanocapsule. Both options fulfill the Wade-Mingos counting rules, i.e. 72 CVEs for the closotb. The trapped [Ru5] metallic clusters are proposed to be the first-grown seeds of subsequent formation of the subnanometric RuNP. Moreover, the double role of the nanocapsule in stabilising ∼0.7 nm NPs and also in hosting ultra-small Ru clusters, is unprecedented and may pave the way towards the synthesis of ultra-small metallic clusters for catalytic purposes.

Recent Advances in the Design and Syntheses of Porphyrinoids by Embedding Higher Analogues of Arene and Pyridine Units.

Due to enthralling applications in various fields and augmenting fundamental wisdom, π-conjugated macrocycles in general and porphyrin systems in particular are constantly explored. Subtle modifications of porphyrin structure can amend the rudimentary properties. Pursuing innovative properties provides impetus to underpin arene or pyridine moiety embedded porphyrin derivatives. There have been several reviews related to arene incorporated carbaporphyrinoids; however, recent developments of porphyrin analogues by introducing higher analogues of arenes and pyridine units are not adequately inspected. This mini-review mainly focuses on biphenyl, bipyridine, terphenyl, and mixed arene pyridine embedded porphyrin analogues and their coordination chemistry.

Assessment of antiproliferative activity of new half‐sandwich arene Ru (II) furylbenzhydrazone complexes

AbstractThe study attempts in finding an effective anticancer activity of six new arene ruthenium (II) complexes possessing the composition of [(η6‐arene)Ru(L)Cl] (arene = benzene (1–3) /p‐cymene (4–6); L = 2‐furyl methyl benzhydrazones). Elemental analysis, Fourier transform infrared spectroscopy (FT‐IR), UV–vis, nuclear magnetic resonance (NMR), and high resolution mass spectrometry (HR‐MS) techniques were utilized to study the synthesized complexes. The single crystal X‐ray crystallography validated the bidentate mode of coordination of the benzhydrazone ligand and pseudo‐octahedral geometry around ruthenium ion. MTT assay has been performed to assess the in vitro growth of cancer cell inhibition ability of all the complexes against MCF‐7(breast carcinoma), HuH‐7 (hepatocellular carcinoma), and HeLa (cervical cancer), along with non‐cancerous L132 (human lung epithelium) cell lines. It has been found that all the six complexes exhibit good to excellent cytotoxicity toward the cancer cell lines tested with low IC50 values compared to cisplatin. Among the synthesized complexes, complex 6 shows potential cytotoxicity against all the cancer cell lines. The observed higher cytotoxicity of the complex 6 may be due to the electron donating methoxy group of the ligand and hydrophobic character of arene moiety. Eventually, the staining techniques such as AO‐EB, HOECHST 33342, RH‐123, and reactive oxygen species (ROS) establish that all the complexes bring about cell death via apoptosis. The present research results emphasize the more possibility to promote potential arene ruthenium anticancer agents.

Equilibrium and Computational Chemical Modelling Studies for the Removal of Methyl Orange and Methyl Red Dyes from Water Using Modified Silica Resin

ABSTRACT This study describes the removal of methyl orange (MO) and methyl red (MR) dyes from water samples using morpholinomethylcalix[4]arene immobilised silica (MIS) resin. The silica surface has been modified by p-morpholinomethylcalix[4]arene moiety and was characterised by FT-IR spectroscopy and SEM techniques. The adsorption capacity of MIS-resin was checked through batch adsorption experiments under the optimised conditions of pH, MIS-resin dose, time, and temperature. Results show that adsorption of MO and MR dyes are highly affected by the change in pH; thus, the higher adsorption percentages were achieved at pH 5.3 and 6.6 respectively. The adsorbent dosage has been optimised and it was noticed that the maximum adsorption was achieved by using 40 mg.L−1 of MIS-resin dose. The adsorption rate of dyes was investigated by applying the pseudo-first and second-order kinetic models and it has been observed that the experimental data shows a better correlation coefficient with the pseudo-second-order kinetic model. The feasibility of adsorption was analysed by thermodynamic parameters such as ∆H°, ∆G°, and ∆S° values indicate that the adsorption of dyes is exothermic and spontaneous. The equilibrium data have been validated using Langmuir and Freundlich models and the Langmuir model has a good correlation coefficient (R2 0.99). The MIS-resin was applied onto industrial effluents and it has been observed that the prepared resin is a very efficient adsorbent for the treatment of dyes contaminated wastewater. The adsorption of MO and MR dyes onto MIS-resin was well defined by computational chemical modelling at the B3LYP/LANL2DZ/6-311++G (d,p) level using G09W software.

Calix[n]arene-based immunogens: A new non-proteic strategy for anti-cocaine vaccine

IntroductionCocaine use disorder is a significant public health issue without a current specific approved treatment. Among different approaches to this disorder, it is possible to highlight a promising immunologic strategy in which an immunogenic agent may reduce the reinforcing effects of the drug if they are able to yield sufficient specific antibodies capable to bind cocaine and/or its psychoactive metabolites before entering into the brain. Several carriers have been investigated in the anti-cocaine vaccine development; however, they generally present a very complex chemical structure, which potentially hampers the proper assessment of the coupling efficiency between the hapten units and the protein structure. ObjectivesThe present study reports the design, synthesis and preclinical evaluation of two novel calix[n]arene-based anti-cocaine immunogens (herein named as V4N2 and V8N2) by the tethering of the hydrolysis-tolerant hapten GNE (15) on calix[4]arene and calix[8]arene moieties. MethodsThe preclinical assessment corresponded to the immunogenicity and dose–response evaluation of V4N2 and V8N2. The potential of the produced antibodies to reduce the passage of cocaine analogue through the blood–brain-barrier (BBB), modifying its biodistribution was also investigated. ResultsBoth calix[n]arene-based immunogens elicited high titers of cocaine antibodies that modified the biodistribution of a cocaine radiolabeled analogue (99mTc-TRODAT-1) and decreased cocaine-induced behavior, according to an animal model. ConclusionThe present results demonstrate the potential of V4N2 and V8N2 as immunogens for the treatment of cocaine use disorder.

Rhodium and Iridium Complexes Bearing “Capping Arene” Ligands: Synthesis and Characterization

A series of olefin-coordinated RhI and IrI complexes bearing “capping arene” ligands (5-XFP and 6-XFP, see below) of the general formulas (FP)M(olefin)X, [(FP)M(olefin)2][M(olefin)2X2], and [(FP)M(olefin)2]BF4 (FP = “capping arene” ligands, X = halide or pseudohalide, olefin = ethylene, cyclooctene, (olefin)2 = (C2H4)2 or cyclooctadiene) were synthesized and characterized. Single-crystal X-ray diffraction studies revealed structural differences that are a function of the identity of the capping arene ligand and the metal. For 5-XFP ligands (5-XFP = 1,2-bis(N-7-azaindolyl)-benzene and derivatives with substituents on the arene moiety), the coordination to both Rh and Ir gives rise to complexes that are best described as 16-electron and square planar. For 6-XFP ligands (6-XFP = 8,8′-(1,2-phenylene)diquinoline and derivatives with substituents on the arene moiety), the structures of Rh and Ir complexes are better considered as 18-electron and trigonal bipyramidal due to an η2-C,C interaction between the metal center and the arene group of the capping arene ligand. Variable-temperature 1H NMR spectroscopy studies of ethylene rotation demonstrated that the Ir complexes possess higher activation barriers to rotation in comparison to Rh complexes and the 6-XFP complexes tend to give ethylene higher rotational barriers in comparison to 5-XFP complexes for complexes of the type (FP)Rh(η2-C2H4)Cl. DFT calculations are consistent with enhanced Rh to ethylene π-back-donation for Rh complexes ligated by the 6-XFP ligands in comparison to the 5-XFP ligands.

Organoruthenium (II) complexes featuring pyrazole‐linked thiosemicarbazone ligands: Synthesis, DNA/BSA interactions, molecular docking, and cytotoxicity studies

AbstractA series of pyrazol‐derived thiosemicarbazone ligands (L1–L4) were synthesized and reacted with [Ru(p‐cymene)(μ‐Cl)Cl]2 to yield a series of “piano‐stool”‐type binuclear ruthenium (II)–arene‐thiosemicarbazone complexes (C1–C8) of the general type [(Ru(η6‐p‐cym)L)2(μ‐im/azpy)] Cl1–2 (L = diphenylpyrazole thiosemicarbazone; cym = p‐cymene; im = imidazole; azpy = 4,4′‐azopyridine). The thiosemicarbazone ligands act as N and S donors binding to the Ru(II) center via the imine nitrogen and the thione sulfur atoms. The complexes were characterized by NMR, FTIR, UV–Vis spectroscopy, and ESI+ mass spectrometry. The binding of the complexes to calf thymus deoxyribonucleic acid (CT‐DNA) and bovine serum albumin (BSA) was evaluated, and it has been established that the binuclear complexes have good binding efficacies with DNA (Kb = 104–105 M−1) and BSA (Ka = 105–106 M−1). This is attributed to the arene moieties present in the ligands of the complexes that can have hydrophobic interactions with DNA/BSA. Ethidium bromide (EB) displacement studies and DNA viscosity measurements revealed intercalative interaction of the complexes with DNA. Static interaction of the complexes with BSA was revealed by fluorescence quenching studies. Molecular docking studies confirmed base stacking, H‐bonding, and hydrophobic interactions with the biomolecules. In vitro antiproliferative studies of the complexes affirmed that the complexes are cytotoxic towards the HeLa (human cervical cancer) cell line with IC50 values in range of 17.3–41.3 μM.

Supramolecular interactions in the heteroarylimine-substituted calix[4]arenes: the formation of cyclic dodecanuclear palladium aggregates

ABSTRACT Two new derivatives of calix[4]arene bearing on the upper rim 2-thiopenyl (Thicalix) or 2-pyridyl (Pycalix) Schiff-base substituents have been synthesised and characterised by IR, NMR, MS, and single crystal X-ray diffraction techniques. It was shown that the interaction of Thicalix with the copper(II) and palladium(II) ions is accompanied by hydrolysis of the azomethine bonds with subsequent oxidation of the aminophenolic fragment to diquinone Diquin, while the reaction of potassium tetrachloropalladate(II) with Pycalix results in the formation of metallocompex with 1:2 calix[4]arene/Pd(II) ratio. The single crystal X-ray diffraction analysis of Thicalix (1), the complex [(PdCl2)2(Pycalix)] (2) and Diquin (3) revealed that all compounds form molecular crystals as a result of numerous supramolecular interactions involving C − H···O, C − H···Cl, and C − H···π contacts. For 1 and 3 such interactions result in formation of dimers, while in 2 the dodecanuclear palladium aggregates composed of six calix[4]arene moieties are formed.

Conjugating pillararene dye in dye-sensitized solar cells

Summary The improvement of open-circuit voltage (VOC) is a crucial goal to develop efficient dye-sensitized solar cells (DSSCs). Here, conjugating pillar[5]arene dyes (PPI and PPII) are designed, synthesized, and applied in DSSCs. The presence of pillar[5]arene moiety in the dyes inhibits the dye aggregation and charge recombination in the DSSCs, leading to the enhancement of VOC. PPI with a single D-π-A backbone and a pillar[5]arene moiety achieves a VOC of 715 mV, which is much higher than the reference dye (VOC of 674 mV) with the same D-π-A backbone but no pillar[5]arene moiety. PPII with 2 D-π-A backbones also achieves a VOC of 746 mV and a much higher short-circuit photocurrent (JSC) than the reference dyes. In addition, the host-guest interaction can adjust the VOC and JSC by coupling dye with the imidazolium in electrolyte, as confirmed by the electrolyte engineering.

Fluorescence quenched and boosted by a-PET effect and host−guest complexation respectively in BODIPY-functionalized pillar[5]arene

A BODIPY-functionalized ethoxypillar[5]arene (EtP5-BDP) and a guest compound G containing both of the cyano and triazole moieties were synthesized. The a-PET process between ethoxypillar[5]arene (EtP5) moiety and BODIPY moiety in EtP5-BDP was predicted by DFT/TDDFT calculations before experiment research. It was easier to occur for the a-PET process in polar solvents (e.g. acetone and CH3CN). The fluorescence of BODIPY moiety in EtP5-BDP was quenched to varying degrees in toluene, CHCl3, acetone and CH3CN. Due to the stronger interactions between EtP5 and G in toluene and CHCl3, when guest G was added, the fluorescence emissions of BODIPY moiety in EtP5-BDP in these two solvents were boosted but they still not recovered to the original emission level of BODIPY. Therefore, the electron transfer between EtP5 moiety and BODIPY moiety could be weakened but not inhibited completely by the host−guest complexation of EtP5-BDP and G. The ΔGCS was −0.01, −0.23, −0.40 and −0.42 eV for the PET process from EtP5 moiety to BODIPY moiety in toluene, CHCl3, acetone and CH3CN, respectively. The ECS of EtP5-BDP was lower than S1 energy state of BODIPY in various solvents. The charge transfer efficiencies (ΦCT) from EtP5 moiety to BODIPY moiety in toluene, CHCl3, acetone and CH3CN were 21%, 46%, 64% and 68%, respectively. All the results proved the a-PET process from EtP5 moiety to BODIPY moiety in EtP5-BDP.

IntraMolecular Diels–Alder Reactions of Vinylarenes and Alkynyl Arenes (the IMDAV Reaction)

AbstractThis comprehensive review summarizes the published literature data concerning the intramolecular Diels–Alder reactions of vinylarenes (the IMDAV reaction) and alkynyl arenes from 1970 to 2019, and covers mainly intramolecular [4+2] cycloaddition reactions of vinyl- or acetylene-substituted furans, thiophenes, pyrroles, indoles, imidazoles, benzenes, and naphthalenes, in which the unsaturated substituent is linked directly to an arene moiety. The selected area of the Diels–Alder reaction differs from other forms of [4+2] cycloadditions due to the uniqueness of the diene fragment, which, along with an exocyclic multiple bond, includes the double bond of an aromatic or heteroaromatic nucleus in its system. Thus, during the formation of the [4+2] cycloaddition intermediate, the aromaticity of furan, thiophene and even benzene rings is broken, leading, as a rule, to the formation of heterocyclic structures rarely accessible by other methods, in contrast to the majority of intermolecular Diels–Alder reactions, with the highest degree of chemo-, regio-, and diastereoselectivity. Therefore, the IMDAV approach is often used for the synthesis of naturally occurring and bioactive molecules, which are also discussed in this review alongside other applications of this reaction. Whenever possible, we have tried to avoid examples of radical, photochemical, oxidative, precious-metal-complex-catalyzed cyclizations and other types of formal [4+2] cycloadditions, focusing on thermal Diels–Alder reactions in the first step, according to the classical mechanism. The second stage of the process, aromatization, is unique for many initial substrates, and hence considerable attention in this overview is given to the detailed description of the reaction mechanisms.1 Introduction2 IMDAV Reactions of Vinylfurans2.1 Alkenes as Internal Dienophiles2.2 Alkynes and Allenes as Internal Dienophiles3 IMDAV Reactions of Vinylthiophenes3.1 Alkenes as Internal Dienophiles3.2 Alkynes as Internal Dienophiles4 IMDAV Reactions of Vinylbenzothiophenes5 IMDAV Reactions of Vinylpyrroles6 IMDAV Reactions of Vinylindoles6.1 Alkenes as Internal Dienophiles6.2 Alkynes as Internal Dienophiles7 IMDAV Reactions of Styrenes and Vinylnaphthalenes7.1 Alkenes as Internal Dienophiles7.2 Alkynes as Internal Dienophiles7.3 Alkynes as Internal Dienophiles in Aryl Acetylenes (the Intramolecular Dehydro Diels–Alder Reaction)8 IMDAV Reactions of Vinylimidazoles, Vinylisoxazoles and Vinylpyridines9 Conclusion10 Abbreviations

Metal-dependent selective formation of calix[4]arene assemblies based on dynamic covalent chemistry.

The reaction of calix[4]arene derivatives 1a and 1b bearing four salicylaldehyde moieties with 1,3-propanediamine gave macrocyclic trimers 5a and 5b, respectively, which have intramolecular bridges formed via the flattened cone conformation. In contrast, a capsular-shaped dimeric cage [7a·2Na]2+ was selectively formed when the conformation of the calix[4]arene moiety of 1a was fixed in the spread cone conformation by complexation with Na+ at the lower-rim amide groups.

Conjugates Containing Two and Three Trithiolato-Bridged Dinuclear Ruthenium(II)-Arene Units as In Vitro Antiparasitic and Anticancer Agents.

The synthesis, characterization, and in vitro antiparasitic and anticancer activity evaluation of new conjugates containing two and three dinuclear trithiolato-bridged ruthenium(II)-arene units are presented. Antiparasitic activity was evaluated using transgenic Toxoplasma gondii tachyzoites constitutively expressing β-galactosidase grown in human foreskin fibroblasts (HFF). The compounds inhibited T. gondii proliferation with IC50 values ranging from 90 to 539 nM, and seven derivatives displayed IC50 values lower than the reference compound pyrimethamine, which is currently used for treatment of toxoplasmosis. Overall, compound flexibility and size impacted on the anti-Toxoplasma activity. The anticancer activity of 14 compounds was assessed against cancer cell lines A2780, A2780cisR (human ovarian cisplatin sensitive and resistant), A24, (D-)A24cisPt8.0 (human lung adenocarcinoma cells wild type and cisPt resistant subline). The compounds displayed IC50 values ranging from 23 to 650 nM. In A2780cisR, A24 and (D-)A24cisPt8.0 cells, all compounds were considerably more cytotoxic than cisplatin, with IC50 values lower by two orders of magnitude. Irrespective of the nature of the connectors (alkyl/aryl) or the numbers of the di-ruthenium units (two/three), ester conjugates 6–10 and 20 exhibited similar antiproliferative profiles, and were more cytotoxic than amide analogues 11–14, 23, and 24. Polynuclear conjugates with multiple trithiolato-bridged di-ruthenium(II)-arene moieties deserve further investigation.