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The synthesis of amides holds great promise owing to their impeccable contributions as building blocks for highly valued functional derivatives. Herein, we disclose the design, synthesis and crystal structure of a mixed-ligand ruthenium(II) complex, [Ru(η6-Cym)(O,O-PLY)Cl], (1) where Cym = 1-isopropyl-4-methyl-benzene and O,O-PLY = deprotonated form of 9-hydroxy phenalenone (HO,O-PLY). The complex catalyzes the aerobic oxidation of various primary amines (RCH2NH2) to value-added amides (RCONH2) with excellent selectivity and efficiency under relatively mild conditions with common organic functional group tolerance. Structural, electrochemical, spectroscopic, and computational studies substantiate that the synergism between the redox-active ruthenium and π-Lewis acidic PLY moieties facilitate the catalytic oxidation of amines to amides. Additionally, the isolation and characterization of key intermediates during catalysis confirm two successive dehydrogenation steps leading to nitrile, which subsequently transform to the desired amide through hydration. The present synthetic approach is also extended to substitution-dependent tuning at PLY to tune the electronic nature of 1 and to assess substituent-mediated catalytic performance. The effect of substitution at the PLY moiety (5th position) leads to structural isomers, which were further evaluated for the catalytic transformations of amine to amides under similar reaction conditions. [ABSTRACT FROM AUTHOR]

Metallo-supramolecular polyelectrolytes (MEPE) have a variety of attractive properties concerning electrochromism, spin-crossover, rheology, and cell differentiation. Previous studies suggest that these polynuclear structures can be regarded as an assembly of individual subunits and mononuclear complexes can act as models. In this study, we synthesize a monotopic and a ditopic terpyridine ligand with pyridinium units as well as the corresponding iron and ruthenium MEPEs and their mononuclear counterparts. UV-vis studies show that the mononuclear complexes have similar absorption properties to MEPEs. Furthermore, all complexes and MEPEs exhibit electrochromic behavior. Yet only the MEPEs can be deposited on different substrates using a layer-by-layer approach which makes them attractive for applications as electrochromic devices. However, the low solubility particularly of the ruthenium MEPE, renders characterization in solution impractical. Hence, the use of mononuclear complexes with similar monotopic ligands as presented herein can act as a first instance to evaluate the properties of corresponding MEPEs, facilitating the development of metallo-supramolecular materials. [ABSTRACT FROM AUTHOR]

Five cationic ruthenium(II) chelates with the generic formula [Ru(S2C·NHC)3](PF6)2 were readily obtained upon cleavage of the [RuCl2(p-cymene)]2 dimer with representative imidazol(in)ium-2-dithiocarboxylate zwitterions (NHC·CS2) in the presence of KPF6. The homoleptic complexes were fully characterized by various analytical techniques and the molecular structure of one of them was determined by single-crystal X-ray diffraction analysis. As expected, it featured an octahedral RuS6 core surrounded by three imidazol(in)ium rings and their nitrogen substituents. The robustness of the Ru–S bonds combined with the chelate effect of the κ2-S,S′-dithiocarboxylate units and the steric protection imparted by bulky 1,3-diarylimidazol(in)ium groups most likely accounted for the outstanding stability of these species in solution. Cyclic voltammetry showed that the five homoleptic complexes featured characteristic waves for a monoelectronic redox process corresponding to the RuIII/RuII couple with E1/2 values ranging between 0.97 and 1.27 V vs. Ag/AgCl. This half-wave potential was clearly dependent on the nature of their ancillary ligands as the evolution of the Ep,ox values roughly paralleled the basicity sequence of the NHCs used to prepare them, in line with the trends observed when monitoring the chemical shifts of the CS2− unit on 13C NMR spectroscopy and the CS2− asymmetric stretching vibration wavenumbers on IR spectroscopy. [ABSTRACT FROM AUTHOR]

To gain mechanistic insights into the acetate-assisted cyclometallations of arylimines promoted by [RuCl2(p-cymene)]2 in polar protic media, DFT geometry optimizations (with M06 and ωB97X-D3 functionals and the cc-pVDZ-PP[Ru] basis set) followed by DLPNO-CCSD(T)/CBS energy evaluations were performed using benzaldimine as a model substrate and methanol as the solvent (with CPCM or SMD models). The calculation results show that coordination of the imine to an acetate ruthenium precursor is followed by anion (chloride or acetate) dissociation as the rate-determining step of the process. H-Bonding of two explicit MeOH to the anion reduces the calculated activation energy to ca. 23 kcal mol−1, in good agreement with the experimental half-life at room temperature. Subsequent AMLA/CMD C–H activation of the intermediate cationic complexes is a faster, reversible process. Alternative reaction pathways involving neutral diacetate ruthenium complexes offer AMLA/CMD transition state structures of lower energy but are precluded due to higher energy barriers for the initial ligand exchange processes at ruthenium. Solvent assistance accelerates the final chloride/acetate exchange processes on the cycloruthenate intermediates, particularly when compression in the condensed phase is taken into consideration. The performance of six DFT functionals (with the aug-pVTZ-PP[Ru] basis set) was assessed using the DLPNO-CCSD(T)/CBS reference energies. Neutral diacetate ruthenium complexes were incorrectly predicted as being kinetically relevant when using hybrid DFT methods (PBE0-D3(BJ), M06-2X or ωB97M-V). Good agreement between the calculated barrier heights and our benchmark energy results was obtained by using double-hybrid DFT methods. PWPB95 with D3(BJ) or D4 dispersion energy corrections was found to be the most accurate (ΔG≠ MUE of ca. 1 kcal mol−1). This study may aid our understanding of and help with further experimental investigations of synthetically useful carboxylate-assisted C–H bond functionalizations involving (N,C)-cyclometallated (p-cymene)Ru(II) intermediate complexes in sustainable polar protic solvents. [ABSTRACT FROM AUTHOR]

Photodynamic therapy is an emerging tumor therapy that kills tumor cells by activating reactive oxygen species (ROS) produced by photosensitizers. Mitochondria, as an important organelle, are the main generator of cellular ROS. Therefore, the development of photosensitizers capable of targeting mitochondria could significantly enhance the efficacy of photodynamic therapy. In this study, two novel ruthenium(II) complexes, Ru-1 and Ru-2, were designed and synthesized, both of which were functionalized with α,β-unsaturated ketones for sensing of glutathione (GSH). The crystal structures of the two complexes were determined and they exhibited good recognition of GSH by off–on luminescence signals. The complex Ru-2 containing aromatic naphthalene can enter the cells and react with GSH to generate a strong luminescence signal that can be used to monitor intracellular GSH levels through imaging. Ru-2 also has an excellent mitochondrial localization ability with a Pearson's coefficient of 0.95, which demonstrates that it can efficiently target the mitochondria of tumor cells to enhance the effectiveness of photodynamic therapy as a photosensitizer. [ABSTRACT FROM AUTHOR]

There are few literature reports on using precatalysts based on ruthenium(II / III) ions in the polymerization of olefins. Therefore, a new coordination compound was designed based on ruthenium(III) ion and 2-phenylpyridine. The resulting monocrystal was characterized by X-ray diffraction (XRD), solid-state (photo)IR spectroscopy, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The new ruthenium(III) complex compound was used as a precatalyst in the oligomerization reactions of ethylene, 2-propen-1-ol, 2-chloro-2-propen-1-ol, 3-butene-2-ol and 2,3-dibromo-2-propen-1-ol with methylaluminoxane and ethylaluminium dichloride as activators. The catalytic activity of the newly discovered ruthenium(III) complex compound ranges from 159.5 (for 2-chloro-2-propen-1-ol) to 755.6 (for ethylene) g mmol−1 h−1 bar−1, indicating that it is a chemical compound with high catalytic activity. In addition, the oligomerization reaction products were subjected to physicochemical characterization, using BET (Brunauer–Emmett–Teller isotherm), mass spectrometry (MALDI-TOF-MS), Fourier transform infrared (FT-IR) spectroscopy, NMR, TGA, differential scanning calorimetry (DSC), and the morphology of the porous polymeric materials was investigated by SEM. The distinguishing feature of the obtained precatalyst is its high catalytic activity under mild reaction conditions, a rare phenomenon. Compared with other precatalysts, it is the most active ruthenium(II / III) ion-based catalytic material used in oligo- and polymerization reactions of ethylene. [ABSTRACT FROM AUTHOR]

The stepwise addition of increasing amounts of Au(PPh3)Cl to [HRu4(CO)12]3− (1) results in the sequential formation of [HRu4(CO)12(AuPPh3)]2− (2), [HRu4(CO)12(AuPPh3)2]− (3), and HRu4(CO)12(AuPPh3)3 (4). Alternatively, 4 can be obtained upon addition of HBF4·Et2O (two mole equivalents) to 3. Further addition of acid to 3 (three mole equivalents) results in the formation of the tetra-aurated cluster Ru4(CO)12(AuPPh3)4 (5). Compounds 2–5 have been characterized by IR, 1H and 31P{1H} NMR spectroscopies. Moreover, the molecular structures of 3–5 have been determined by single crystal X-ray diffraction as [NEt4][3]·2CH2Cl2, 4-b·2CH2Cl2, 4-a, 5·0.5CH2Cl2·solv, and 5·solv crystalline solids. Two different isomers of 4, that is 4-a and 4-b, have been crystallographically characterized and their rapid interconversion in solution was studied by variable temperature 1H and 31P{1H} NMR spectroscopies. Weak aurophilic Au⋯Au contacts have been detected in the solid state structures of 3–5. Computational studies have been performed in order to elucidate bonding and isomerism, as well as to predict the possible structure of the elusive species 2. [ABSTRACT FROM AUTHOR]

Two rigid β-elimination immune PCcarbeneP pincer ligands, differing in their electron donor properties by variation of the substitution pattern on the aromatic linker arms, were complexed to ruthenium to form the dichlorides LRRuCl2 (R = H or NMe2). These compounds were converted to hydrido chlorides by treatment with dihydrogen (H2) and a base. By converting to tert-butoxide derivatives in situ under an atmosphere of H2, the poly hydride PCalkylP complexes LHRRu(H)3 compounds were generated. In these complexes, H2 has added across the Ru＝C bond in the PCcarbeneP starting materials. The polyhydrides are dynamic in solution and extensive NMR studies helped to elucidate the speciation and fluxional processes operative in this dynamic system. The polyhydride complexes react rapidly with CO2 to give the PCcarbeneP formato hydride complexes LRRu(H)-κ2-O2CH. For R = H, the 1,2-hydride shift from the anchoring alkyl of the PCalkylP carbon to the metal is reversible, but for R = NMe2 it is irreversible. The CO2 incorporated into the formato ligand of these compounds exchanges with free CO2via a bimolecular mechanism that is more rapid for R = NMe2 than for R = H; plausible explanations for this observation are proffered. Experiments designed to evaluate the efficacy of the R = NMe2 formato hydride complex as a catalyst precursor for CO2 hydrogenation to formate salts reveal poor performance in comparison to state-of-the-art ruthenium-based catalysts. This is due primarily to the precipitation of a dimeric μ-κ2-κ1-CO3 carbonate complex that is not an active catalyst for the reaction. [ABSTRACT FROM AUTHOR]

The article deals with the development of isomeric ruthenium(II)–hydrido complexes [RuII(H)(L1)(PPh3)2(CO)]ClO4 ([1a]ClO4–[1b]ClO4)/[RuII(H)(L2)(PPh3)2(CO)]ClO4 ([2a]ClO4–[2b]ClO4) involving azo coupled L1 [L1: (E)-1,2-bis(1-methyl-1H-pyrazol-3-yl)diazene]/L2 [L2: (E)-1,2-bis(4-iodo-1-methyl-1H-pyrazol-3-yl)diazene], respectively. Structural evaluation of the complexes affirmed the syn conformation of the coordinated/uncoordinated pyrazole groups of L and its unperturbed neutral azo (N＝N) state. Isomeric forms in [1a]ClO4/[1b]ClO4 or [2a]ClO4/[2b]ClO4 differed with respect to the cis and trans orientations of the coordinated CO and N(azo) donor of L, respectively. It also demonstrated the formation of intermolecular hydrogen-bonded dimeric or 1D-polymeric chains in [1a]ClO4/[2b]ClO4 or [1b]ClO4, respectively. Successive two-electron reductions of the complexes varied to an appreciable extent as a function of the heterocycles connected to L. The involvement of the azo function of L towards the reductions ([N＝N]0 → [N＝N]˙− → [N＝N]2−) was supported by the DFT calculated MOs and Mulliken spin density at the paramagnetic state, which was further validated by the radical EPR profile of the first reduced (S = 1/2) state. Isomeric [1a]ClO4/[1b]ClO4 or [2a]ClO4/[2b]ClO4 immobilised on the carbon cloth support underwent various electrochemical acidic HERs (hydrogen evolution reactions) with TOF/10−1 s−1: [1a]ClO4 (0.83) > [1b]ClO4 (0.68) > [2a]ClO4 (0.50) > [2b]ClO4 (0.37). [ABSTRACT FROM AUTHOR]

Two rigid β-elimination immune PCcarbeneP pincer ligands, differing in their electron donor properties by variation of the substitution pattern on the aromatic linker arms, were complexed to ruthenium to form the dichlorides LRRuCl2 (R = H or NMe2). These compounds were converted to hydrido chlorides by treatment with dihydrogen (H2) and a base. By converting to tert-butoxide derivatives in situ under an atmosphere of H2, the poly hydride PCalkylP complexes LHRRu(H)3 compounds were generated. In these complexes, H2 has added across the Ru＝C bond in the PCcarbeneP starting materials. The polyhydrides are dynamic in solution and extensive NMR studies helped to elucidate the speciation and fluxional processes operative in this dynamic system. The polyhydride complexes react rapidly with CO2 to give the PCcarbeneP formato hydride complexes LRRu(H)-κ2-O2CH. For R = H, the 1,2-hydride shift from the anchoring alkyl of the PCalkylP carbon to the metal is reversible, but for R = NMe2 it is irreversible. The CO2 incorporated into the formato ligand of these compounds exchanges with free CO2via a bimolecular mechanism that is more rapid for R = NMe2 than for R = H; plausible explanations for this observation are proffered. Experiments designed to evaluate the efficacy of the R = NMe2 formato hydride complex as a catalyst precursor for CO2 hydrogenation to formate salts reveal poor performance in comparison to state-of-the-art ruthenium-based catalysts. This is due primarily to the precipitation of a dimeric μ-κ2-κ1-CO3 carbonate complex that is not an active catalyst for the reaction. [ABSTRACT FROM AUTHOR]

Ru(II) complexes with polypyridyl ligands (2,2′-bipyridine = bpy, 1,10-phenanthroline = phen) play a central role in the development of photocatalytic organic reactions. In this work, we synthesized four mixed-ligand [Ru(phen)(bpy)2]2+-type complexes (Ru-Pcat-A) bearing two phosphonate substituents P(O)(OH)(OR) (R = H, Et) attached to the phen core at positions 3,8 (Ru-3,8PH and Ru-3,8PHEt) and 4,7 (Ru-4,7PH and Ru-4,7PHEt) of the heterocycle in high yields (87–99%) and characterized them using spectral methods. Single crystal X-ray diffraction was employed to determine the coordination mode of the ditopic phen ligand in Ru-4,7PH. This complex exists as the neutral species and forms a 1D hydrogen-bonded framework in the crystals. The light absorption characteristics were found to be similar for all complexes prepared in this work. However, the emission maxima in aqueous solutions were significantly affected by the substitution of the heterocycle, ranging from 629 nm for Ru-4,7PH to 661 nm for Ru-3,8PHEt. The emission quantum yields in Ar-saturated deionized water showed a strong dependence on the substitution pattern of the phen ligand, with maximal values reaching approximately 0.11 for Ru-4,7PHEt and Ru-4,7PH, which is twice as high as that of the classical [Ru(bpy)3]2+ complex (Ru-bpy). The photocatalytic performance of Ru-Pcat-A was investigated using visible light photoredox catalytic transformations of tertiary amines. With Ru-Pcat-A, we achieved the phosphonylation of N-aryl-1,2,3,4-tetrahydroisoquinolines (THIQs) and cyanation of THIQs and N,N-dimethylaniline in methanol, while a mixture of nitromethane/methanol (1 : 1 v/v) proved to be the optimal solvent for conducting the nitromethylation of THIQs. In the majority of the studied reactions, Ru-4,7PHEt exhibited greater efficiency compared to Ru-bpy, and it could be easily separated from the products using water extraction and reused in the next catalytic cycle. We successfully performed seven consecutive nitromethylation and phosphonylation of N-phenyl-1,2,3,4-tetrahydroisoquinoline using the recycled homogeneous photoredox catalyst. [ABSTRACT FROM AUTHOR]

Complexes PyrDPE-RuCl and PyrDPE-Ruacac with a π-extended 2,7-di(4-phenylethynyl)pyrene linker undergo simultaneous one-electron oxidations of their {Ru}-styryl entities. The absence of an intervalence charge-transfer (IVCT) band at intermediate stages, where the mixed-valent, singly oxidized radical cation is present, and spin density confinement to the terminal styryl ruthenium site(s) are tokens of a lack of electronic coupling between the {Ru} entities across the π-conjugated linker. The close similarity of the linker-based π → π* bands in the complexes and the free ligand and their insensitivity towards oxidations at the terminal sites indicate that the central pyrenyl fluorophore is electronically decoupled from the electron-rich {Ru}-styryl termini. As a consequence, the complexes offer stable pyrene-based fluorescence emissions at 77 K, which are red-shifted from that of the linker. [ABSTRACT FROM AUTHOR]

New 1,2-azolylamidino complexes fac-[RuCl(DMSO)3(NHC(R)az*-κ²N,N)]OTf [R = Me (2), Ph (3); az* = pz (pyrazolyl, a), indz (indazolyl, b)] are synthesized via chloride abstraction from their corresponding precursors cis,fac-[RuCl2(DMSO)3(az*H)] (1) after subsequent base-catalyzed coupling of the appropriate nitrile with the 1,2-azole previously coordinated. All the compounds are characterized by ¹H NMR, 13C NMR and IR spectroscopy. Those derived from MeCN are also characterized by X-ray diffraction. Electrochemical studies showed several reduction waves in the range of −1.5 to −3 V. The electrochemical behavior in CO2 media is consistent with CO2 electrocatalytic reduction. The catalytic activity expressed as [icat(CO2)/ip(Ar)] ranged from 1.7 to 3.7 for the 1,2-azolylamidino complexes at voltages of ca. −2.7 to −3 V vs. ferrocene/ferrocenium. Controlled potential electrolysis showed rapid decomposition of the Ru catalysts. Photocatalytic CO2 reduction experiments using compounds 1b, 2b and 3b carried out in a CO2-saturated MeCN/TEOA (4 : 1 v/v) solution containing a mixture of the catalyst and [Ru(bipy)3]2+ as the photosensitizer under continuous irradiation (light intensity of 150 mW cm−2 at 25 °C, λ > 300 nm) show that compounds 1b, 2b and 3b allowed CO2 reduction catalysis, producing CO and trace amounts of formate. The combined turnover number for the production of formate and CO is ca. 100 after 8 h and follows the order 1b < 2b ≈ 3b. [ABSTRACT FROM AUTHOR]

An unexpected reversal in catalytic activity for acceptorless dehydrogenative coupling compared to acceptorless alcohol dehydrogenation has been observed using a series of cationic Ru(II)–CNC pincer complexes with different ancillary ligands. In continuation of our study of cationic Ru(II)–CNC pincer complexes 1a–6a, new complexes with bulky N-wingtips [Ru(CNCiPr)(CO)(PPh3)Br]PF6 (1b), [Ru(CNCCy)(CO)(PPh3)Cl]PF6 (1c), [Ru(CNCCy)(CO)(PPh3)H]PF6 (2c), [Ru(CNCiPr)(PPh3)2Cl]PF6 (3b), [Ru(CNCCy)(PPh3)2Cl]PF6 (3c), [Ru(CNCiPr)(PPh3)2H]PF6 (4b), [Ru(CNCCy)(PPh3)2H]PF6 (4c), [Ru(CNCiPr)(DMSO)2Cl]PF6 (6b), and [Ru(CNCCy)(DMSO)2Cl]PF6 (6c) [CNCR = 2,6-bis(1-alkylimidazol-2-ylidene)-pyridine] have been synthesized and the catalytic activities of the new complexes have been compared with their N-methyl analogues for transfer hydrogenation of cyclohexanone and acceptorless dehydrogenation of benzyl alcohol. Furthermore, all complexes have been utilized as catalysts in the dehydrogenative coupling reaction of benzyl alcohol with amines. While the catalytic activities of the new complexes for transfer hydrogenation and acceptorless alcohol dehydrogenation were found to be in line with the previously observed trend based on the ancillary ligands (CO > COD > DMSO > PPh3), for the acceptorless dehydrogenative coupling reaction, complexes containing PPh3 and DMSO ligands performed better compared to complexes containing CO and COD ligands. Based on NMR and mass investigation of catalytic reactions, a plausible mechanism has been suggested to explain the difference in catalytic activity and its reversal during the dehydrogenative coupling reaction. Furthermore, the substrate scope for the dehydrogenative coupling reaction of benzyl alcohol with a wide range of amines has been explored, including synthesizing some pharmaceutically important imines. All new complexes have been characterized by various spectroscopic techniques, and the structures of 4b and 6b have been confirmed by the single-crystal X-ray diffraction technique. [ABSTRACT FROM AUTHOR]

Carbon materials have a very wide range of applications in the field of electrocatalysis, both as catalyst bodies and as excellent supports for catalysts. In this work, we obtained a graphitic-like orange-peel derived carbon (OPC) material through pre-carbonization and KOH activation strategies using discarded orange-peel as a raw material. OPC has good graphitization characteristics and a few-layer structure, making it very suitable as a support for nanoparticle catalysts. In order to compare the performance of OPC, we used commercial graphene as the benchmark, made two carbon materials uniformly loaded with ruthenium nanoparticles under the same conditions, and obtained two HER catalysts (Ru/OPC and Ru/rGO). The results indicate that Ru/OPC has excellent HER catalytic performance under alkaline conditions, not only superior to Ru/rGO, but also surpassing commercial Pt/C. In 1 M KOH; the overpotential of Ru/OPC is only 3 mV at −10 mA cm−2, greatly exceeding those of Ru/rGO (100 mV) and Pt/C (31 mV). Under high current density (j), the performance of Ru/OPC is even better; the overpotential is 79 mV and 136 mV at −100 mA cm−2 and −200 mA cm−2, respectively. More importantly, Ru/OPC also has a very high TOF and long-term stability, with a TOF of up to 10.62 H2 s−1 at an overpotential of 100 mV and almost no attenuation after 72 h of operation at −50 mA cm−2. Ru/OPC also exhibits good catalytic performance under acidic conditions, significantly superior to that of Ru/rGO. For Ru/OPC, the overpotential is 86 mV, 167 mV and 214 mV at −10 mA cm−2, −100 mA cm−2 and −200 mA cm−2, respectively. Under the same conditions, the overpotential of Ru/rGO is 143 mV, 253 mV and 306 mV at −10 mA cm−2, −100 mA cm−2 and −200 mA cm−2, respectively. [ABSTRACT FROM AUTHOR]

Hydrogen economy has emerged as a promising alternative to the current hydrocarbon economy. It involves harvesting renewable energy to split water into hydrogen and oxygen and then further utilising clean hydrogen fuel for various applications. The rational exploration of advanced non-precious metal bifunctional electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is critical for efficient water splitting. Herein, an ultralow Ru-modified cobalt metal–organic framework (CoRu0.06-MOF/NF) two-dimensional nanosheet array bifunctional catalyst was fabricated through a strategy under mild experimental conditions. The obtained CoRu0.06-MOF/NF exhibited excellent bifunctional electrocatalytic activity and stability in alkaline media, with low overpotentials of 37 and 181 mV and significant durability for more than 95 and 110 h toward the HER and OER at 10 mA cm−2, respectively. The experimental results showed that the two-dimensional nanoarray structure had a large specific surface area and abundant exposed active sites. Additionally, ultralow Ru modification optimized the electronic structure and improved the conductivity of the cobalt metal–organic frameworks, thereby reducing the energy barrier of the rate-limiting step and accelerating the water splitting reaction. [ABSTRACT FROM AUTHOR]

On the basis of our previous comparative studies on the DNA binding of a pair of ruthenium(II) complex enantiomers, Δ-[Ru(bpy)2PBIP]2+ and Λ-[Ru(bpy)2PBIP]2+ {bpy = 2,2′-bipyridine, PBIP = 2-(4-bromophenyl)imidazo[4,5-f]1,10-phenanthroline}, in this study, their antitumor activities and mechanisms were further investigated comparatively. The cytotoxicity assay demonstrated that both the enantiomers exerted selective antiproliferative effects on cancer cell lines A2780 and PC3. Fluorescence localization experiments suggested that both the enantiomers effectively permeated the nucleus of HeLa cells and co-localized with DNA, resulting in their DNA damage and apoptosis. Flow cytometry experiments showed that the apoptosis was enhanced by increasing the concentration of each enantiomer. Western blotting analyses indicated that both extrinsic and intrinsic apoptosis pathways were activated by the two enantiomers. miRNA microarray analyses displayed that both the enantiomers up- and downregulated multiple miRNAs, some of which were predicted to be associated with carcinogenesis. The above experimental results also showed that the Δ-enantiomer exerted a more potent antitumor activity, a higher efficiency of entering cancer cells and a stronger apoptosis-inducing effect compared with the Λ-enantiomer. Combined with the previously published research results, experimental results from this study implied that the antitumor activity of a metal complex might have originated from the conformation change of DNA in tumor cells caused by the intercalation of the complex, that the antitumor mechanism of a metal complex could be related to its DNA-binding mode, and that the antitumor efficiency of a metal complex could result from its DNA-binding strength. [ABSTRACT FROM AUTHOR]

Electron-withdrawing nitro-substituents were installed onto terpyridine- and phenanthroline-based metallosurfactants with 4d6 ruthenium(II), which were deposited as Langmuir–Blodgett monolayers aiming to study the feasibility of charge transport in Au‖LB‖Au junctions. The nitro groups are intended to modulate the energy of the frontier molecular orbitals to near to, or match that of Fermi levels in the gold electrodes. A series of heteroleptic metallosurfactants [RuII(C18OPh-terpy)(X-terpy)](PF6)2 and [RuII(C18OPh-terpy)(X-phen)Cl]PF6 were synthesized, where C18OPh-terpy is the 4′-[4-(octadecyloxy)phenyl]-2,2′:6′,2′′-terpyridine amphiphile common to all species, X-terpy is a terpyridine with—H (1) or—phenyl-NO2 (2) and X-phen is a phenanthroline with—H (3) or—NO2 (4) groups. These metallosurfactants were characterized by experimental and computational methods, and the presence of nitro groups affect more affordable reductions at less negative potentials, as well as slightly more positive oxidations, these changes are less pronounced in species 2 than in 4. Species 1 and 2 showed limited Pockels-Langmuir and Langmuir–Blodgett film formation with lower collapse pressure of 27 mN m−1. In contrast, metallosurfactants 3 and 4 showed enhanced hydrophilicity indicated by higher collapse pressures of ca. 36 mN m−1. The LB monolayers of 3 and 4 were deposited on gold electrodes to form Au‖LB‖Au junctions and electron transport was measured as I/V curves. The NO2-bearing species 4 showed asymmetric curves associated with directional electron transport with amplitudes up to −2.0 nA and rectification ratios from 5 to 26 between −1 to +1 V and from 3 to 14 between −3 to +3 V. [ABSTRACT FROM AUTHOR]

Ruthenium(II) polypyridyl complexes have drawn growing attention due to their photophysical properties and anticancer activity. Herein we report four ruthenium(II) polypyridyl complexes [(N^N)2RuII(L)]2+ (1–4, L = 4-anilinoquinazoline derivatives, N^N = bidentate ligands with bis-nitrogen donors) as multi-functional anticancer agents. The epidermal growth factor receptor (EGFR) is overexpressed in a broad range of cancer cells and related to many kinds of malignance. EGFR inhibitors, such as gefitinib and erlotinib, have been approved as clinical anticancer drugs. The EGFR-inhibiting 4-anilinoquinazoline ligands greatly enhanced the in vitro anticancer activity of these ruthenium(II) polypyridyl complexes against a series of human cancer cell lines compared to [Ru(bpy)2(phen)], but interestingly, these complexes were actually not potent EGFR inhibitors. Further mechanism studies revealed that upon irradiation with visible light, complexes 3 and 4 generated a high level of singlet oxygen (1O2), and their in vitro anticancer activities against human non-small-cell lung (A549), cervical (HeLa) and squamous (A431) cancer cells were significantly improved. Specifically, complex 3 displayed potent phototoxicity upon irradiation with blue light, of which the photo-toxicity indexes (PIs) against HeLa and A431 cells were 11 and 8.3, respectively. These complexes exhibited strong fluorescence emission at ca. 600 nm upon excitation at about 450 nm. A subcellular distribution study by fluorescence microscopy imaging and secondary ion mass spectrometry imaging (ToF-SIMS) demonstrated that complex 3 mainly localized at the cytoplasm and complex 4 mainly localized in the nuclei of cells. Competitive binding with ctDNA showed that complex 4 was more favorable to bind to the DNA minor groove than complex 3. These differences support that complex 3 possibly exerts its anticancer activities majorly by photo-induced 1O2 generation and complex 4 by binding to DNA. [ABSTRACT FROM AUTHOR]

A new series of cationic ruthenium(II) complexes, [RuCl(PPh3)2(κ3-NNN-L1)]Cl (1), [RuH(PPh3)2(κ3-NNN-L2)]Cl (2), and [RuH(PPh3)2(κ3-NNN-L3)]Cl (3), bearing a 2,6-bis (1-R-5-methyl-pyrazol-3-yl) pyridine ligand (L1: R = H, L2: R = C6H4-p-CF3, L3: R = C6H4-p-OCH3), were synthesized and characterized with NMR, HRMS, and single-crystal X-ray diffraction. Their catalytic application was investigated in the acceptorless dehydrogenation (AD) of primary alcohols. Complex 1 outperformed 2 and 3 in terms of the selectivity towards the aldehydes, and provided the aldehydes with a yield of up to 99%, with good functional group tolerance under mild conditions. In addition, the only by-product of the reaction was dihydrogen, which can be collected as clean energy, and the reaction meets the requirements of environment-friendly chemistry. Complex 1 also proved to be a promising catalyst in the sequential AD/condensation reaction between the primary and secondary alcohols, affording α,β-unsaturated ketones in moderate to good selectivity. [ABSTRACT FROM AUTHOR]

Ruthenium-based complexes have been suggested as promising anticancer drugs exhibiting reduced general toxicity compared to platinum-based drugs. In particular, Ru(η6-arene)(PTA)Cl2 (PTA = 1,3,5-triaza-7-phosphaadamantane), or RAPTA, complexes have demonstrated efficacy against breast cancer by suppressing metastasis, tumorigenicity, and inhibiting the replication of the human tumor suppressor gene BRCA1. However, RAPTA compounds have limited cytotoxicity, and therefore comparatively high doses are required. This study explores the activity of a series of RAPTA-like ruthenium(II) arene compounds against MCF-7 and MDA-MB-231 breast cancer cell lines and [Ru(η6-toluene)(PPh3)2Cl]+ was identified as a promising candidate. Notably, [Ru(η6-toluene)(PPh3)2Cl]Cl was found to be remarkably stable and highly cytotoxic, and selective to breast cancer cells. The minor groove of DNA was identified as a relevant target. [ABSTRACT FROM AUTHOR]

Irradiation of [Ru(GaCp*)3(SiEt3)H3] (1) at 350 nm induces reductive elimination of dihydrogen and triethylsilane and generates unsaturated Ru/Ga species. This photochemically induced cascading reductive elimination processes generate the reactive intermediate [Ru(GaCp*)3], which can be trapped by diphosphine coordination to yield the stable complex [(dppe)Ru(GaCp*)3] (4). The photochemically generated RuGa3 species is catalytically active in the hydrogenation of alkynes, which is further investigated by 1H NMR and mass spectrometry. Formation of intermetallic Ru/Ga clusters is observed as a competing and for the catalytic activity of the species limiting side reaction. [ABSTRACT FROM AUTHOR]

A series of saturated ruthenium cluster carbonyls (Ru(CO)5+, Ru2(CO)9+, Ru3(CO)12+, Ru4(CO)14+, Ru5(CO)16+ and Ru6(CO)18+) have been synthesized in the gas phase and subsequently characterized by infrared spectroscopy. Their size-specific IR spectra in the region of the carbonyl stretch vibration (1900–2150 cm−1) and in the region of the Ru–C–O bending modes (420–620 cm−1) are obtained by infrared multiple photon dissociation spectroscopy. The structures of these cluster carbonyls are assigned by comparison with results from density functional calculations. A multitude of differently activated CO ligands are identified in these cationic cluster carbonyls, reaching from terminal, over non-symmetrically bridging (semi-bridging) ligands with varying degrees of interaction to additional Ru atoms towards symmetrically bridging CO ligands. [ABSTRACT FROM AUTHOR]

We describe the synthesis, physicochemical characterization, and in vitro antitumor assays of four novel analogous ruthenium(II) complexes with general formula cis-[RuII(N-L)(P-P)2]PF6, where P-P = bis(diphenylphosphine)methane (dppm, in complexes 1 and 2) or bis(diphenylphosphine)ethane (dppe, in complexes 3 and 4) and N-L = 5,6-diphenyl-4,5-dihydro-2H-[1,2,4]triazine-3-thione (Btsc, in complexes 1 and 3) or 5,6-diphenyltriazine-3-one (Bsc, in complexes 2 and 4). The data were consistent with cis arrangement of the biphosphine ligands. For the Btsc and Bsc ligands, the data pointed to monoanionic bidentate coordination to ruthenium(II) through N,S and N,O, respectively. Single-crystal X-ray diffraction showed that complex 1 crystallized in the monoclinic system, space group P21/c. Determination of the cytotoxicity profiles of complexes 1–4 gave SI values ranging from 1.19 to 3.50 against the human lung adenocarcinoma cell line A549 and the non-tumor lung cell line MRC-5. Although the molecular docking studies suggested that the interaction between DNA and complex 4 was energetically favorable, the experimental results showed that they interacted weakly. Overall, our results demonstrated that these novel ruthenium(II) complexes have interesting in vitro antitumor potential and this study may contribute to further studies in medicinal inorganic chemistry. [ABSTRACT FROM AUTHOR]

Electrocatalyst design is an important approach to prompt the commercialization of water electrolysis technologies. In this work, a ruthenium doped MoS2/AB heterostructure is synthesized as an electrocatalyst for the hydrogen evolution reaction (HER) through hydrothermal and annealing processes. The physical–chemical characterization studies show that the MoS2/AB heterostructure and the incorporation of Ru effectively induce a phase transition from 2H to 1T-MoS2. The as-prepared Ru-MoS2/AB exhibits an excellent HER performance with a very low overpotential of 13 mV at 10 mA cm−2 and a Tafel slope of 31 mV dec−1 in 0.5 M H2SO4, remarkably higher than those of Pt/C (overpotential of 28 mV at 10 mA cm−2, 41 mV dec−1). Density functional theory calculations suggest that the H absorption on Ru bonding to S exhibits a rather low binding energy (−0.22 eV), indicating the optimum active sites of Ru near S for HER. Significantly, the Ru-MoS2/AB also demonstrates high stability under long-term discharge and elevated temperature conditions. These results suggest that the as-prepared Ru-MoS2/AB can be a promising alternative to Pt/C for water electrolysis, due to its high HER activity, easy synthesis, and good stability. [ABSTRACT FROM AUTHOR]

The electrocatalytic properties of Ru complexes are of great technological interest given their potential application in reactions such water splitting and CO2 reduction. In this work, a novel terpyridine-based Ru(II) complex, [RuCl(trpy)(acpy)], trpy = 2,2′:6′,2′′-terpyridine, acpy− = 2-pyridylacetate was synthesized and its spectroscopic, electrochemical and catalytic properties were explored in detail. In dry acetonitrile, the complex exhibits two reduction peaks at −1.95 V and −2.20 V vs. Fc/Fc+, attributed to consecutive 1 e− reduction. Under CO2 atmosphere, a catalytic wave is observed (Eonset = 2.1 V vs. Fc/Fc+), with CO as the main reduction product. Bulk electrolysis reveals a turnover number (TON) of 12 (kobs = 1.5 s−1). In the presence of 1% water, an improvement in the catalytic activity is observed (TONCO = 21 and kobs = 2.0 s−1) and, additionally, formate was also detected (TONHCOO = 7). Spectroelectrochemical experiments allowed the identification of a metallocarboxylate (Ru–COO−) intermediate under anhydrous conditions, while in water, the partial labilization of the acpy− ligand was observed in the course of the catalytic cycle. The experimental data was combined with DFT calculations, allowing the proposal of a catalytic cycle. The results establish important relationships between selectivity, ligand structure and reaction conditions. [ABSTRACT FROM AUTHOR]

In these studies, we designed and investigated cyto- and genotoxic potential of five ruthenium cyclopentadienyl complexes bearing different phosphine and phosphite ligands. All of the complexes were characterized with spectroscopic analysis (NMR, FT-IR, ESI-MS, UV-vis, fluorescence and XRD (for two compounds)). For biological studies, we used three types of cells – normal peripheral blood mononuclear (PBM) cells, leukemic HL-60 cells and doxorubicin-resistance HL-60 cells (HL-60/DR). We compared the results obtained with those obtained for the complex with maleimide ligand CpRu(CO)2(η1-N-maleimidato) 1, which we had previously reported. We observed that the complexes CpRu(CO)(PPh3)(η1-N-maleimidato) 2a and CpRu(CO)(P(OEt)3)(η1-N-maleimidato) 3a were the most cytotoxic for HL-60 cells and non-cytotoxic for normal PBM cells. However, complex 1 was more cytotoxic for HL-60 cells than complexes 2a and 3a (IC50 = 6.39 μM vs. IC50 = 21.48 μM and IC50 = 12.25 μM, respectively). The complex CpRu(CO)(P(OPh)3)(η1-N-maleimidato) 3b is the most cytotoxic for HL-60/DR cells (IC50 = 104.35 μM). We found the genotoxic potential of complexes 2a and 3a only in HL-60 cells. These complexes also induced apoptosis in HL-60 cells. Docking studies showed that complexes 2a and CpRu(CO)(P(Fu)3)(η1-N-maleimidato) 2b have a small ability to degrade DNA, but they may cause a defect in DNA damage repair mechanisms leading to cell death. This hypothesis is corroborated with the results obtained in the plasmid relaxation assay in which ruthenium complexes bearing phosphine and phosphite ligands induce DNA breaks. [ABSTRACT FROM AUTHOR]

A red emissive ruthenium(II) complex 1[PF6]2 of an amino ethanol substituted 1,10-phenanthroline-based ligand (L1) has been developed and characterized by spectroscopic analysis and single-crystal X-ray diffraction. Complex 1 shows an aggregation-induced emission (AIE) enhancement and forms nano-aggregates in the poor solvent water and highly dense polyethylene glycol (PEG) media. The possible reason behind the AIE properties may be the rigidity gained through weak supramolecular interactions between neighbouring phenanthroline ligands and PF6− counterions. The AIE properties were supported by UV-vis and photoluminescence (PL) spectroscopy and dynamic light scattering (DLS) studies to substantiate the formation of nano-aggregates and to understand the morphology of the aggregated particles, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies were performed. Compound 1[PF6]2 was highly selective towards pyrophosphate ions (PPi) over other phosphates such as ATP, ADP, AMP and H2PO4− ions and other competitive anions in the PL spectroscopic channel in acetonitrile. The PL titrations of 1[PF6]2 with PPi in CH3CN furnished the association constant Ka = 1.08 × 104 M−1 and the detection limit was calculated as low as 1.54 μM. The PPi detection has been established through the unique H-bonding interaction, supported by 1H NMR titration. Finally, the cytotoxicity study and bioimaging were carried out for biological application. The complex shows very low cytotoxicity and good biocompatibility and is suitable for intracellular PPi imaging. [ABSTRACT FROM AUTHOR]

This paper presents the synthesis and structural characterization of a series of new ruthenium(II) complexes 1–7, with the general formula mer-[RuL3(N–N)Cl]Cl, where L is 2,2′:6′,2′′-terpyridine (tpy) or 4′-(4-chlorophenyl)-2,2′:6′,2′′-terpyridine (Cl-Ph-tpy) and N–N is o-benzoquinonediimine (o-bqdi), 2,3-naphthoquinonediimine (nqdi), 4,4′-dimethyl-2,2′-bipyridine (dmbpy) or 2,2′-bipyridine-4,4′-dicarboxylic acid (dcbpy). The kinetic results showed that the ligand substitution reactions of new Ru(II)-polypyridyl complexes with biomolecules were affected by different substituents and the aromaticity of meridional tridentate and bidentate spectator ligands as well as by the nature of the entering nucleophile. The reactivity of the complexes increases in the order: dmbpy < dcbipy < nqdi < o-bqdi. In addition, quantum chemical calculations were performed to support the interpretation and discussion of the experimental data. Furthermore, combining ethidium bromide (EB) and Hoechst 33258 (2-(4-hydroxyphenyl)-5-[5-(4-methylpiperazine-1-yl)benzimidazo-2-yl]-benzimidazole) fluorescence assay results implied that 1–7 might interact with calf thymus DNA through partial intercalation and/or minor groove binding. The human serum albumin (HAS)-fluorescence binding studies involving the site markers, eosin Y, as a marker for site I of subdomain IIA, and ibuprofen, as a marker for site II of subdomain IIIA, showed that Ru(II) compounds bind to both sites with moderately strong affinity (Kb = 104–106 M−1). Moreover, these DNA/HSA experimental results were confirmed by molecular docking. Complexes 2, 5 and 6 exerted good to strong and highly selective cytotoxic activity against breast adenocarcinoma (MDA-MB 231), colorectal carcinoma (HCT116) and cervix adenocarcinoma (HeLa). Depending on their structure and cell line, the complexes acted differently in terms of their influence on autophagy, the cell cycle and the engaged apoptotic pathway. [ABSTRACT FROM AUTHOR]

The first examples of Bi(III) and Sb(III) halide compounds combined with a photoswitchable ruthenium nitrosyl unit are reported. The structures of [RuNOPy4Br]4[Sb2Br8][Sb3Br12]2 (1) and (H3O)[RuNOPy4Br]4[Bi2Br9]3·3H2O (2) were determined by X-ray diffraction, and exhibit three different structural types of group 15 halometalates. Low-temperature IR-spectroscopy measurements reveal that the irradiation of 1 at 365 nm switches a stable Ru–NO (GS) unit to a metastable Ru–ON (MS1) linkage. Moreover, the light excitation of 2 at 365 or 405 nm induces the additional formation of a side-bond isomer Ru-η2-(NO) (MS2). The reverse reactions MS1/MS2 → GS can be induced by red–infrared light irradiation or by heating at temperatures >200 K. The obtained synthetic and spectroscopic data open the way for the preparation of hybrid halide complexes with a variety of photoswitchable complexes (NO2, SO2, N2, etc.), and give an insight into the behavior of light-induced species embedded in polynuclear halides. [ABSTRACT FROM AUTHOR]

A ruthenium nitrosyl complex (1·NO) and 1·NO incorporated phospholipid-based liposomes (Lip-1·NO) were reported for highly selective colorimetric detection of H2S. The probe 1·NO "cross-talks" with H2S and releases nitric oxide (NO) in the process. The detection limit for H2S was found to be 0.31 μM and 0.45 μM in the cases of 1·NO and Lip-1·NO, respectively. The DAF-FM DA assay has been performed to confirm the H2S-induced NO release from 1·NO and Lip-1·NO. The sensing of H2S was also verified by ESI-MS and FT-IR spectroscopy. It was also observed that external stimuli, H2S and light worked in an almost similar way to release NO as observed by UV-Vis spectroscopy. A molecular logic gate operation "OR" was applied to the probe 1·NO in combination with inputs 'light' and 'H2S' to give the output 'NO release'. Hence, the probe 1·NO performs the dual work of sensing H2S with a colorimetric response, releasing NO upon cross-talk between NO and H2S. [ABSTRACT FROM AUTHOR]

Multifunctional switches are crucial to the development of smart molecular materials and molecular-electronic applications. Here, we describe the synthesis, structure, and characterization of several spiropyrans functionalized with alkynyl-[Ru(dppe)2] moieties. Through electrochemical and spectroelectrochemical studies, we demonstrate access to several stable redox states, in addition to states accessed via acidochromism and photoisomerisation. Initial protonation was found to occur at the alkynyl functionality followed by acid-induced ring-opening of the spiropyran ligand to form the protonated merocyanine. The protonated merocyanine can be switched from the Z- to E-isomer by using ultraviolet light. The spiropyran was also shown to be an effective insulator for electronic communication across the molecular backbone. [ABSTRACT FROM AUTHOR]

In comparison with RuII-arene compounds, the medicinal potential of homologous RuII-tpm compounds [tpm = tris(pyrazolyl)methane] is underexplored. Pyridine, 4-pyridinemethanol and four functionalized pyridines, synthesized from the esterification of 4-pyridinemethanol with bioactive carboxylic acids (i.e., ethacrynic acid, ibuprofen, flurbiprofen and naproxen), react with the precursor [RuCl(κ3-tpm)(PPh3)2]Cl (1) to afford [RuCl(κ3-tpm)(PPh3)(L)]Cl (2–7, L = pyridine ligand), in 78–91% yields. All products were fully characterized by HR-ESI mass spectrometry, IR and multinuclear NMR spectroscopy and the solid-state structures of two of the complexes, i.e. where L = pyridine and 4-pyridinemethanol, were ascertained by single crystal X-ray diffraction. The {Ru-tpm-PPh3} assembly is stable in D2O and in biological medium (DMEM) at 37 °C, with a tendency to slowly dissociate the pyridine ligand. The antiproliferative activity of the complexes was assessed on the cancerous A2780 and A2780cisR cell lines, and the nontumoral HEK 293T cell line; moreover inhibition assays were carried out on the complexes towards COX-2 and GSTP1 enzymes. [ABSTRACT FROM AUTHOR]

The coordination of the B–H bond to a transition metal is fundamentally intriguing due to its connection with the transition metal-mediated B–H bond activation mechanism and catalysis. Most of the reported examples are σ-borane/borate complexes containing one or two σ-B–H bonds. However, examples of compounds containing three σ-B–H bonds are still much rarer. Herein, we report a facile approach for the synthesis of rare transition metal tris(σ-B–H) borate complexes by the salt elimination protocol using [Cp*RuCl]4 and lithium trihydroborates Li[ArBH3] containing 2,6-disubstituted aryl groups. These complexes have remarkable thermal stability in solution. In addition, this novel class of compounds has the unusual σ-complex that features three labile σ-B–H bonds. Our studies on these new species demonstrate that the coordination σ-B–H bond can undergo H/D exchange with D2 and ligand substitution reactions with PPh3, PCy3 and IPr2Me2. These results provide new approaches for the synthesis of both tris(σ-B–H) borates and bis(σ-B–H) borates. [ABSTRACT FROM AUTHOR]

The chemotherapeutic potential of ruthenium(II) complexes has recently attracted researchers' interest as antibacterial and anticancer agents. In this study, two novel half-sandwich imine-based Ru complexes ([Ru(p-cymene)Cl(L-1)][PF6] (Ru-1) and [Ru(p-cymene)Cl(L-2)][PF6] (Ru-2)) were reported for their deoxyribonucleic acid (DNA) binding and antitubercular, antibacterial, and anticancer activities. The molecular structure of Ru-2 was obtained by single-crystal X-ray crystallography. DNA interaction studies were conducted by UV-Vis absorbance and fluorescence spectral titration which gave rise to DNA binding constants (Kb) of 1.32 × 106 and 1.82 × 106 for Ru-1 and Ru-2, respectively and the Stern–Volmer binding constant (KSV) values for Ru-1 and Ru-2 were 1.7763 × 104 M−1 and 7.6 × 103 M−1, respectively. The in vitro antitubercular activity was evaluated against Mycobacterium tuberculosis H37Ra. The antibacterial potential of both the Ru-complexes was examined against Gram-negative (Escherichia coli and Pseudomonas aeruginosa) and Gram-positive (Staphylococcus aureus and Bacillus subtilis) bacteria. The half-maximal inhibitory concentration (IC50) values for the antitubercular activity of Ru-1 and Ru-2 were 4.87 ± 1.32 μM and 5.78 ± 0.54 μM, respectively. A cytotoxic study of these complexes was performed against the human breast cancer cell line (MCF-7) and the human embryonic kidney cell line (HEK293) (normal cells). The study revealed meaningful activity of the Ru-1 complex against (cancer) MCF-7 cells, while the viability of HEK293 (normal) cells in the presence of Ru-2 was higher as compared to a reference drug 5FU. We suggest that these kinds of Ru-complexes could have potential for application in metallopharmaceuticals. [ABSTRACT FROM AUTHOR]

106Ru is a radioactive isotope usually generated by the nuclear industry within power plant reactors. During a nuclear accident, 106Ru reacts with oxygen, leading to the production of highly volatile ruthenium tetroxide RuO4. The combination of volatility and radioactivity makes 106RuO4, one of the most radiotoxic species and justifies the development of a specific setup for its capture and immobilization. In this study, we report for the first time the capture and immobilization of gaseous RuO4 within a porous metal–organic framework (UiO-66-NH2). We used specific installation for the production of gaseous RuO4 as well as for the quantification of this gas trapped within the filtering medium. We proved that UiO-66-NH2 has remarkable affinity for RuO4 capture, as this MOF exhibited the worldwide highest RuO4 decontamination factor (DF of 5745), hundreds of times higher than the DF values of sorbents daily used by the nuclear industry (zeolites or activated charcoal). The efficiency of UiO-66-NH2 can be explained by its pore diameters well adapted to the capture and immobilization of RuO4 as well as its conversion into stable RuO2 within the pores. This conversion corresponds to the reactivity of RuO4 with the MOF organic sub-network, leading to the oxidation of terephthalate ligands. As proved by powder X-ray diffraction and NMR techniques, these modifications did not decompose the MOF structure. [ABSTRACT FROM AUTHOR]

A mononuclear iridium-based complex with a primary amine group (named Ir–NH2), a mononuclear ruthenium-based complex with a butanoic acid group (named Ru–COOH) and the corresponding heterodinuclear complex containing an iridium and ruthenium center via an amide bond bridge (named Ir–Ru) were designed and successfully synthesized in this study. The photophysical and electrochemical properties and ECL performances of these three metal complexes under various experimental conditions were well characterized. For the first time, the insights from this comprehensive comparison study indicate that the two metal-based subunits with comparable luminescent properties are significant in the design of bimetallic-based multicolor luminophores at the molecular level, which helps us to further understand the emission performances of bimetallic complexes and to rationally design more efficient corresponding organometallic luminophores with multicolor emission for wide applications in the future. [ABSTRACT FROM AUTHOR]

Since the discovery of the numerous physiological roles exhibited by nitric oxide (NO), ruthenium nitrosyl (RuNO) complexes have been regarded as one of the most promising NO donors, stable, well tolerated by the body and capable of releasing NO locally and quantitatively, under light irradiation. This release can be achieved by two-photon absorption (TPA) processes, which allow the irradiation to be performed in the near infrared domain, where light has its maximum depth of penetration in biological tissues. This review provides a short introduction on the biological properties of NO, on RuNO complexes with photo-releasing capabilities, and on the origin of TPA properties in molecules. Then, the RuNO complexes with TPA capabilities are thoroughly discussed either as monometallic or polymetallic species. [ABSTRACT FROM AUTHOR]

The synthesis, photophysics, and electrochemiluminescence (ECL) of four water-soluble dinuclear Ir(III) and Ru(II) complexes (1–4) terminally-capped by 4′-phenyl-2,2′:6′,2′′-terpyridine (tpy) or 1,3-di(pyrid-2-yl)-4,6-dimethylbenzene (N^C^N) ligands and linked by a 2,7-bis(2,2′:6′,2′′-terpyridyl)fluorene with oligoether chains on C9 are reported. The impact of the tpy or N^C^N ligands and metal centers on the photophysical properties of 1–4 was assessed by spectroscopic methods including UV-vis absorption, emission, and transient absorption, and by time-dependent density functional theory (TDDFT) calculations. These complexes exhibited distinct singlet and triplet excited-state properties upon variation of the terminal-capping terdentate ligands and the metal centers. The ECL properties of complexes 1–3 with better water solubility were investigated in neutral phosphate buffer solutions (PBS) by adding tripropylamine (TPA) as a co-reactant, and the observed ECL intensity followed the descending order of 3 > 1 > 2. Complex 3 bearing the [Ru(tpy)2]2+ units displayed more pronounced ECL signals, giving its analogues great potential for further ECL study. [ABSTRACT FROM AUTHOR]

Ru(II) complexes with polypyridyl ligands play a central role in the development of photocatalytic organic reactions. This work is aimed at the structural modification of such complexes to increase their photocatalytic efficiency and adapt them for the preparation of reusable photocatalytic systems. Nine [Ru(phen)(bpy)2]2+-type complexes (bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) (Ru-Pcat) bearing the P(O)(OEt)2 substituent attached to the phen core directly or through a 1,4-phenylene linker were synthesized and characterized by spectroscopic and electrochemical techniques. The coordination mode of phen ligands was confirmed by single crystal X-ray analysis. The (spectro)electrochemical data show that the first electron transfer in Ru-Pcat takes place on the phen ligand. The emission maxima and quantum yields are strongly affected by the substitution pattern, reaching the far-red region (697 nm) for Ru-3,8P2. The singlet oxygen quantum yields of Ru-Pcat were evaluated using the chemical trapping method. Finally, the photocatalytic performance of Ru-Pcat in the oxidation of sulfides with molecular oxygen was investigated. Both dialkyl and alkyl aryl sulfides were quantitatively transformed into sulfoxides under irradiation with a blue LED in the acetonitrile–water mixture (10 : 1) using a low loading of 0.005–0.05 mol% Ru(II) photocatalysts. To rationalize the effect of phosphonate substituents on the photocatalytic efficiency, comparative kinetic studies of (1) 4-nitrothioanisole oxidation proceeding predominantly via the electron transfer pathway and (2) oxidation of dibutyl sulfide wherein singlet oxygen serves as an oxidant have been performed. It was demonstrated that complexes with the P(O)(OEt)2 substituent at positions 4 and 7 outperform the benchmark photocatalyst Ru-(bpy)3 and the parent complex Ru-phen in the reactions proceeding through electron transfer (reductive quenching photocatalytic cycle). The TON in the oxidation of 4-methoxythioanisole was found to be as high as 1 000 000 that is, to our knowledge, the highest among previously reported photocatalysts. In contrast, upon separating the P(O)(OEt)2 group and the phen core with the 1,4-phenylene linker, singlet oxygen quantum yields significantly increase that favors reactions proceeding through energy transfer (the oxidation of dibutyl sulfide in our case). Thus, both series of Ru(II) complexes prepared in this work are promising for the improvement of known photocatalytic reactions and the development of new transformations. [ABSTRACT FROM AUTHOR]

As an ideal scaffold for metal ion chelation, 8-hydroxyquinoline (8HQ) can chelate different metal ions, such as Fe2+, Cu2+, Zn2+, etc. Here, by integrating 8HQ with a ruthenium(II) polypyridyl moiety, two Ru(II)-8HQ complexes (Ru1 and Ru2), [Ru(N–N)2L](PF6)2 (L = 2-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)quinolin-8-ol; N–N: 2,2′-bipyridine (bpy, in Ru1), 1,10-phenanthroline (phen, in Ru2)) were designed and synthesized. In both complexes, ligand L is an 8HQ derivative designed to chelate the cofactor Fe2+ of jumonji C domain-containing demethylase (JMJD). As expected, Ru1 and Ru2 could inhibit the activity of JMJD by chelating the key cofactor Fe2+ of JMJD, resulting in the upregulation of histone-methylation levels in human lung cancer (A549) cells, and the upregulation was more pronounced under light conditions. In addition, MTT data showed that Ru1 and Ru2 exhibited lower dark toxicity, and light irradiation could significantly enhance their antitumor activity. The marked photodynamic activities of Ru1 and Ru2 could induce the elevation of reactive oxygen species (ROS), depolarization of mitochondrial membrane potential (MMP), and activation of caspases. These mechanistic studies indicated that Ru1 and Ru2 could induce apoptosis through the combination of JMJD inhibitory and PDT activities, thereby achieving dual antitumor effects. [ABSTRACT FROM AUTHOR]

Molecular trimeric ruthenium carboxylate clusters (Ru3 clusters) have been introduced into the pore channels of mesoporous metal–organic framework chromium terephthalate [MIL-101(Cr)] by employing a facile two-step post-synthetic strategy in which diamine hooks anchored on the framework metal nodes of the MOF are used to covalently immobilize the Ru3 clusters. The catalytic activity of the isolated Ru3 clusters in the pore channels of the MOF was significantly improved compared to the bulk counterpart. [ABSTRACT FROM AUTHOR]

In this work, four new ruthenium complexes [Ru(η6-p-cymene)(L1)Cl] 1, [Ru(η6-p-cymene)(L2)Cl] 2, [Ru(η6-p-cymene)(L3)Cl] 3 and [Ru(η6-p-cymene)(L4)Cl] 4 [HL1 = (2-cyanophenyl)glycine; HL2 = (5-chloro-2-cyanophenyl)glycine; HL3 = (2-cyano-3-fluorophenyl)glycine; HL4 = (4-cyanophenyl)glycine] were synthesized and well characterized by several spectroscopic and analytical techniques. Complexes 1 and 3 were found to be fluorescent in most of the solvents; however, 2 and 4 were found to be fluorescent mostly in EtOAc, DMF and ethanol. Amongst these four complexes, 3 has shown selective sensing against CO32− and SO42− anions by quenching of fluorescence. The LOD values are found to be in the sub-micromolar range. Investigations of the sensing mechanism performed by computation and NMR studies indicate a possible adduct formation between the NH group of the ligand and the anion(s) through hydrogen bond formation, which ultimately might lead to proton transfer to the bi-negative anion. The quantum yield of the complex 3 was found to decrease on addition of CO32− and SO42− anions from 0.46 to 0.13 and 0.12, respectively. The Job's plot indicates the binding between the probe and anion in a 1 : 1 ratio for both CO32− and SO42− anions. Along with that, all the complexes were found to be biocompatible when tested against several cell lines showing very high IC50 values. It can also be observed that 1 is capable of penetrating within the cells and can act as a cell imaging agent showing fluorescence, and thus can be used for bio-imaging purposes. [ABSTRACT FROM AUTHOR]

Long triplet lifetimes of excited photosensitizers are essential for efficient energy transfer reactions in water, given that the concentrations of dissolved oxygen and suitable acceptors in aqueous media are typically much lower than in organic solvents. Herein, we report the design, synthesis and photochemical characterization of two structurally related water-soluble ruthenium complex-based dyads decorated with a covalently attached pyrene chromophore. The triplet energy of the latter is slightly below that of the metal complex enabling a so-called triplet reservoir and excited-state lifetime extensions of up to two orders of magnitude. The diimine co-ligands, which can be modified easily, have a major impact on both the ultrafast intramolecular energy transfer (iEnT) kinetics upon excitation with visible light and the lifetime of the resulting long-lived pyrene triplet. The phenanthroline-containing dyad shows fast triplet pyrene formation (25 ps) and an exceptionally long triplet lifetime beyond 50 microseconds in neat water. The iEnT process via the Dexter mechanism is slower by a factor of two when bipyridine co-ligands are employed, which is rationalized by a poor orbital overlap. Both dyads are very efficient sensitizers for the formation of singlet oxygen in air-saturated water as well as for the bimolecular generation of anthracene triplets that are key intermediates in upconversion mechanisms. This is demonstrated by the 5-hydroxymethylfurfural oxidation, which yields completely different main products depending on the pH value of the aqueous solution, as an initial application-related experiment and by time-resolved spectroscopy. Our findings are important in the greater contexts of photocatalysis and energy conversion in the "green" solvent water. [ABSTRACT FROM AUTHOR]

The present work aimed to obtain discrete heavier metal complexes of unperturbed deprotonated bis-lawsone (hinge-like H2L = 2,2′-bis(3-hydroxy-1,4-napthoquinone). This is primarily due to its limited examples with lighter metal ions (Co, Zn, and Ga) and the fact that our earlier approach with the osmium ion facilitated its functionalisation. Herein, we demonstrated the successful synthesis and structural characterisation of L2−-derived diruthenium [(bpy)2RuII(μ-L2−)RuII(bpy)2](ClO4)2 [1](ClO4)2 (S = 0), (acac)2RuIII(μ-L2−)RuIII(acac)22 (S = 1) and monoruthenium (pap)2Ru(L2−) 3 (S = 0) derivatives (bpy = 2,2′-bipyridine, acac = acetylacetonate, and pap = 2-phenylazopyridine). The crystal structures established that (i) O,O−/O,O− donating five-membered bis-bidentate and O−,O− donating seven-membered bidentate chelating modes of deprotonated L2− in rac (ΔΔ/ΛΛ) diastereomeric [1](ClO4)2, 2 and 3, respectively. (ii) The L2− bridging unit in [1](ClO4)2, 2 and 3 underwent twisting its two naphthoquinone rings with respect to the ring connecting C–C bond by 73.01°, 62.15° and 59.12°, respectively. (iii) Intermolecular π–π interactions (∼3.5 Å) between the neighbouring molecules. The paramagnetic complex 2 (S = 1) with two non-interacting Ru(III) (S = 1/2) ions exhibited weak antiferromagnetic coupling only at very low temperatures. In agreement with the magnetic results, 2 displayed typical RuIII-based anisotropic EPR in CH3CN (/Δg: 2.314/0.564) but without any forbidden g1/2 signal at 120 K. The complexes exhibited multiple redox processes in CH3CN in the experimental potential window of ± 2.0 V versus SCE. The analysis of the redox steps via a combined experimental and theoretical (DFT/TD-DFT) approach revealed the involvement of L2− to varying extents in both the oxidative and reductive processes as a consequence of its bidirectional redox non-innocent feature. The mixing of the frontier orbitals of the metal ion and L2− due to their closeness in energy indeed led to the resonating electronic form in certain redox states instead of any precise electronic structural state. [ABSTRACT FROM AUTHOR]

Two multichromophoric homoleptic ruthenium(II) complexes [Ru(tpy-BODIPY)2]Cl2 (complexes 1 and 2, tpy = 4-phenyl-2,2:6,2-terpyridine, BODIPY = boron-dipyrromethene) were prepared, characterized and their phototherapeutic activity and bioimaging properties were studied. The complexes having structural similarity differ only by a phenylethynyl linker, and its overall influence on their physicochemical and photobiological behavior was evaluated. The terpyridine-BODIPY ligand L1 was structurally characterized by X-ray crystallography. The complexes showed intense absorption near 500 nm (ε: ∼1.5 × 105 M−1 cm−1 in DMSO), have a high singlet oxygen quantum yield (ΦΔ: ∼0.6 in DMSO), and displayed low photobleaching thus making them suitable for PDT applications. The complexes showed high DNA binding affinity and induced DNA damage on light activation via multiple types of ROS production. Confocal laser scanning microscopy experiments revealed their incorporation in the cancer cells and complex 1 predominantly accumulated in lysosomes. The complexes displayed a significant PDT effect in cancerous cells with visible light activation with a high photocytotoxicity index (PI) value in HeLa cells. Both type-I and type-II photosensitization processes were involved in the PDT effect. The photodynamic action of complex 2 initiated cellular apoptosis. Finally, their diagnostic potential was evaluated against clinically relevant 3D multicellular tumor spheroids (MCTs). [ABSTRACT FROM AUTHOR]

Ruthenium polypyridyl complexes have gained significant interest as photochemotherapies (PCTs) where their excited-state properties play a critical role in the photo-cytotoxicity mechanism and efficacy. Herein we report a systematic electrochemical, spectrochemical, and photophysical analysis of a series of ruthenium(II) polypyridyl complexes of the type [Ru(bpy)2(N–N)]2+ (where bpy = 2,2′-bipyridine; N–N is a bidentate polypyridyl ligand) designed to mimic PCTs. In this series, the N–N ligand was modified through increased conjugation and/or incorporation of electronegative heteroatoms to shift the metal-to-ligand charge-transfer (MLCT) absorptions near the therapeutic window for PCTs (600–1100 nm) while incorporating steric bulk to trigger photoinduced ligand dissociation. The lowest energy MLCT absorptions were red-shifted from λmax = 454 nm to 564 nm, with emission energies decreasing from λmax = 620 nm to 850 nm. Photoinduced ligand ejection and temperature-dependent emission studies revealed an important interplay between red-shifting MLCT absorptions and accessing the dissociative 3dd* states, with energy barriers between the 3MLCT* and 3dd* states ranging from 850 cm−1 to 2580 cm−1 for the complexes measured. This work demonstrates the importance of understanding both the MLCT manifold and 3dd* state energy levels in the future design of ligands and complexes for PCT. [ABSTRACT FROM AUTHOR]

Aiming to develop a new class of metallosurfactants with unidirectional electron transfer properties, a (terpyridine) ruthenium complex containing a semiquinone derivative L2, namely [RuIII(Lterpy)(L2)Cl]PF6 (1), was synthesized and structurally characterized as a solid and in solution. The electronic and redox behaviour of 1 was studied experimentally as well as by means of DFT methods, and is indicative of significant orbital mixing and overlap between metal and ligands. The complex forms stable Pockels–Langmuir films at the air-water interface and allows for the formation of thin films onto gold electrodes to prepare nanoscale Au‖LB 1‖Au junctions for current–voltage (I/V) analysis. Complex 1 shows asymmetric electron transfer with a maximum rectification ratio of 32 based on tunnelling through MOs of the aminocatechol derivative. [ABSTRACT FROM AUTHOR]

Electrochemical water splitting constitutes one of the most promising strategies for converting water into hydrogen-based fuels, and this technology is predicted to play a key role in the transition towards a carbon-neutral energy economy. To enable the design of cost-effective electrolysis cells based on this technology, new and more efficient anodes with augmented water splitting activity and stability will be required. Herein, we report an active molecular Ru-based catalyst for electrochemically-driven water oxidation (overpotential of ∼395 mV at pH 7 phosphate buffer) and two simple methods for preparing anodes by attaching this catalyst onto glassy carbon through multi-walled carbon nanotubes to improve stability as well as reactivity. The anodes modified with the molecular catalyst were characterized by a broad toolbox of microscopy and spectroscopy techniques, and interestingly no RuO2 formation was detected during electrocatalysis over 4 h. These results demonstrate that the herein presented strategy can be used to prepare anodes that rival the performance of state-of-the-art metal oxide anodes. [ABSTRACT FROM AUTHOR]

Ruthenium polypyridyl complexes have been widely used as bioprobes and photosensitizers. However, several disadvantages including slow cellular uptake, nonspecific binding with biomolecules and toxicity limit their applications. In this study, a nanocarrier of human serum albumin coated gold nanorods was developed to deliver a ruthenium photosensitizer for PDT/PTT combination therapy. The HSA coating endowed the nanodrug with high biocompatibility and stability under physiological conditions. Ru-GNR-HSANPs generate 1O2 and hydroxyl radicals to kill cancer cells under blue light irradiation, and exhibit excellent photothermal anticancer effects under 808 nm light irradiation. Significant synergistic anticancer effects were achieved by combined PDT/PTT therapy. Importantly, Ru-GNR-HSANPs can have the synergistic PDT/PTT functions with no need of drug release from the carrier. [ABSTRACT FROM AUTHOR]