Arene Ru(II) Complexes Acted as Potential KRAS G-Quadruplex DNA Stabilizer Induced DNA Damage Mediated Apoptosis to Inhibit Breast Cancer Progress

A series of arene Ru(II) complexes, [(η⁶-MeC₆H₅)Ru(L)Cl]Cl, (L=o-ClPIP, 1; m-ClPIP, 2 and p-ClPIP, 3) (o-ClPIP=2-(2-chlorophenyl)imidazo[4,5-f][1,10]phenanthroline; m-ClPIP=2-(3-chlorophenyl)imidazo[4,5-f][1,10]phenanthroline; p-ClPIP=2-(4-chlorophenyl)imidazo[4,5-f][1,10]phenanthroline) was synthesized and investigated as a potential apoptosis inducer in chemotherapy. Spectroscopy and molecular docking simulations show that 1 exhibits moderated binding affinity to KRAS G-quadruplex DNA by groove mode. Further, in vitro studies reveal that 1 displays inhibitory activity against MCF-7 growth with IC₅₀ = 3.7 ± 0.2 μM. Flow cytometric analysis, comet assay, and immunofluorescence confirm that 1 can induce the apoptosis of MCF-7 cells and G0/G1 phase arrest through DNA damage. In summary, the prepared arene Ru(II) complexes can be developed as a promising candidate for targeting G-quadruplex structure to induce the apoptosis of breast cancer cells via binding and stabilizing KRAS G-quadruplex conformation on oncogene promoter.     

Arene Ruthenium(II) Complexes Bearing the κ-P or κ-P,κ-S Ph2P(CH2)3SPh Ligand

Neutral [Ru(η⁶-arene)Cl₂{Ph₂P(CH₂)₃SPh-κP}] (arene = benzene, indane, 1,2,3,4-tetrahydronaphthalene: 2a, 2c and 2d) and cationic [Ru(η⁶-arene)Cl(Ph₂P(CH₂)₃SPh-κP,κS)]X complexes (arene = mesitylene, 1,4-dihydronaphthalene; X = Cl: 3b, 3e; arene = benzene, mesitylene, indane, 1,2,3,4-tetrahydronaphthalene, and 1,4-dihydronaphthalene; X = PF₆: 4a–4e) complexes were prepared and characterized by elemental analysis, IR, ¹H, ¹³C and ³¹P NMR spectroscopy and also by single-crystal X-ray diffraction analyses. The stability of the complexes has been investigated in DMSO. Complexes have been assessed for their cytotoxic activity against 518A2, 8505C, A253, MCF-7 and SW480 cell lines. Generally, complexes exhibited activity in the lower micromolar range; moreover, they are found to be more active than cisplatin. For the most active ruthenium(II) complex, 4b, bearing mesitylene as ligand, the mechanism of action against 8505C cisplatin resistant cell line was determined. Complex 4b induced apoptosis accompanied by caspase activation.     

Modification of amyloid-beta peptide aggregation via photoactivation of strained Ru(ii) polypyridyl complexes

Alzheimer''s disease (AD) is a chronic neurodegenerative disorder characterized by progressive and irreversible damage to the brain. One of the hallmarks of the disease is the presence of both soluble and insoluble aggregates of the amyloid beta (Aβ) peptide in the brain, and these aggregates are considered central to disease progression. Thus, the development of small molecules capable of modulating Aβ peptide aggregation may provide critical insight into the pathophysiology of AD. In this work we investigate how photoactivation of three distorted Ru(ii) polypyridyl complexes (Ru1–3) alters the aggregation profile of the Aβ peptide. Photoactivation of Ru1–3 results in the loss of a 6,6′-dimethyl-2,2′-bipyridyl (6,6′-dmb) ligand, affording cis-exchangeable coordination sites for binding to the Aβ peptide. Both Ru1 and Ru2 contain an extended planar imidazo[4,5-f][1,10]phenanthroline ligand, as compared to a 2,2′-bipyridine ligand for Ru3, and we show that the presence of the phenanthroline ligand promotes covalent binding to Aβ peptide His residues, and in addition, leads to a pronounced effect on peptide aggregation immediately after photoactivation. Interestingly, all three complexes resulted in a similar aggregate size distribution at 24 h, forming insoluble amorphous aggregates as compared to significant fibril formation for peptide alone. Photoactivation of Ru1–3 in the presence of pre-formed Aβ_1–42 fibrils results in a change to amorphous aggregate morphology, with Ru1 and Ru2 forming large amorphous aggregates immediately after activation. Our results show that photoactivation of Ru1–3 in the presence of either monomeric or fibrillar Aβ_1–42 results in the formation of large amorphous aggregates as a common endpoint, with Ru complexes incorporating the extended phenanthroline ligand accelerating this process and thereby limiting the formation of oligomeric species in the initial stages of the aggregation process that are reported to show considerable toxicity.

Photoactivation of a series of Ru(ii) polypyridyl complexes leads to ligand exchange and modulation of amyloid-beta peptide aggregation of relevance to Alzheimer''s disease.     

Ruthenafuran Complexes Supported by the Bipyridine-Bis(diphenylphosphino)methane Ligand Set: Synthesis and Cytotoxicity Studies

Mononuclear and dinuclear Ru(II) complexes cis-[Ru(κ²-dppm)(bpy)Cl₂] (1), cis-[Ru(κ²-dppe)(bpy)Cl₂] (2) and [Ru₂(bpy)₂(μ-dpam)₂(μ-Cl)₂](Cl)₂ ([3](Cl)₂) were prepared from the reactions between cis(Cl), cis(S)-[Ru(bpy)(dmso-S)₂Cl₂] and diphosphine/diarsine ligands (bpy = 2,2′-bipyridine; dppm = 1,1-bis(diphenylphosphino)methane; dppe = 1,2-bis(diphenylphosphino)ethane; dpam = 1,1-bis(diphenylarsino)methane). While methoxy-substituted ruthenafuran [Ru(bpy)(κ²-dppe)(C^O)]⁺ ([7]⁺; C^O = anionic bidentate [C(OMe)CHC(Ph)O]⁻ chelate) was obtained as the only product in the reaction between 2 and phenyl ynone HC≡C(C=O)Ph in MeOH, replacing 2 with 1 led to the formation of both methoxy-substituted ruthenafuran [Ru(bpy)(κ²-dppm)(C^O)]⁺ ([4]⁺) and phosphonium-ring-fused bicyclic ruthenafuran [Ru(bpy)(P^C^O)Cl]⁺ ([5]⁺; P^C^O = neutral tridentate [(Ph)₂PCH₂P(Ph)₂CCHC(Ph)O] chelate). All of these aforementioned metallafuran complexes were derived from Ru(II)–vinylidene intermediates. The potential applications of these metallafuran complexes as anticancer agents were evaluated by in vitro cytotoxicity studies against cervical carcinoma (HeLa) cancer cell line. All the ruthenafuran complexes were found to be one order of magnitude more cytotoxic than cisplatin, which is one of the metal-based anticancer agents being widely used currently.     

Synthesis,characterization, DNA-binding and DNA-photocleavage studies of [Ru(bpy)2(BPIP)] and [Ru(phen)2(BPIP)] (BPIP = 2-(4′-biphenyl)imidazo[4,5-f][1,10]phenanthroline)

New ligand 2-(4′-biphenyl)imidazo[4,5-f][1,10]phenanthroline (BPIP) and its complexes [Ru(bpy)₂(BPIP)]²⁺ (1) (bpy = 2,2′-bipyridine) and [Ru(phen)₂(BPIP)]²⁺ (2) (phen = 1,10-phenanthroline) have been synthesized and characterized by mass spectroscopy, ¹H NMR and cyclic voltammetry. The interaction of two Ru(II) complexes with calf thymus DNA (CT-DNA) was investigated by spectroscopic and viscosity measurements. Results indicate that both complexes bind to DNA via an intercalative mode and the DNA-binding affinity of complex 2 is much greater than that of complex 1. Furthermore, when irradiated at 365 nm, both complexes have also been found to promote the photocleavage of plasmid pBR 322 DNA.     

Synthesis,characterization and interaction of mixed polypyridyl ruthenium(II) complexes with calf thymus DNA

New mixed polypyridyl {HPIP = 2-(2-hydroxyphenyl)imidazo[4,5-f][1,10]phenanthroline, phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, dmb = 4,4-dimethyl-2,2-bipyridine} ruthenium(II) complexes [Ru(phen)₂(HPIP)]²⁺, [Ru(dmp)₂(HPIP)]²⁺ and [Ru(dmb)₂(HPIP)]²⁺ were synthesized and characterized by elemental analyses ¹H-n.m.r., u.v.–vis. spectroscopy and cyclic voltammetry. Their DNA-binding properties were demonstrated by absorption, luminescence titrations, steady-state emission quenching and viscosity measurements. The results suggested that all the examined complexes bind with CT-DNA intercalatively. Methyl groups substituted at the 4,4-positions of bpy has no obvious effect on its DNA binding, whereas substituents at the 2- and 9-positions of phen have an impressive effect on its DNA-binding, as revealed by the decreased binding affinity.     

Synthesis and Characterization of New Ruthenium (II) Complexes of Stoichiometry [Ru(p-Cymene)Cl2L] and Their Cytotoxicity against HeLa-Type Cancer Cells

When the [Ru(p-cymene)(μ-Cl)Cl]₂ complex is made to react, in dichloromethane, with the following ligands: 2-aminobenzonitrile (2abn), 4-aminobenzonitrile (4abn), 2-aminopyridine (2ampy) and 4-aminopyridine (4ampy), after addition of hexane, the following compounds are obtained: [Ru(p-cymene)Cl₂(2abn)] (I), [Ru(p-cymene)Cl₂(4abn)] (II), [Ru(p-cymene)Cl₂(2ampy] (III) and [Ru(p-cymene)Cl₂(μ-(4ampy)] (IV). All the compounds are characterized by elemental analysis of carbon, hydrogen and nitrogen, proton nuclear magnetic resonance, COSY ¹H-¹H, high-resolution mass spectrometry (ESI), thermogravimetry and single-crystal X-ray diffraction (the crystal structure of III is reported and compared with the closely related literature of II). The cytotoxicity effects of complexes were described for cervical cancer HeLa cells via 3-(4.5-dimethylthiazol-2-yl)-2.5-diphenyltetrazolium bromide (MTT) assay. The results demonstrate a low in vitro anticancer potential of the complexes.     

Luminescent 1,10-Phenanthroline β-Diketonate Europium Complexes with Large Second-Order Nonlinear Optical Properties

Substitution of the diglyme ligand of [Eu(hfa)₃(diglyme)] (where hfa is hexafluoroacetylacetonate) with a simple 1,10-phenanthroline leads to a six-fold increase of the product μβ_EFISH, as measured by the Electric-Field-Induced Second Harmonic generation (EFISH) technique. Similarly, [Eu(tta)₃(1,10-phenanthroline)] (where Htta is 2-thenoyltrifluoroacetone) is characterized by a large second-order NLO response. Both 1,10-phenanthroline europium complexes have great potential as multifunctional materials for photonics.     

An unexpected fluorescent probe for G-quadruplex DNA based on a nitro-substituted ruthenium (II) complex

The detection of G-quadruplex is of major interest. Nitro-substituted ruthenium (II) complexes have attracted much attention due to fluorescent sensitivity to environment change. We report here a new nitro-substituted ruthenium (II) complex, [Ru (phen)₂(hnoip)]²⁺ ( 1) (hnoip = 2-(2-hydroxyl-5-nitrophenyl)imidazo[4,5-f][1,10-phenanthroline]), which displays distinct fluorescent properties in aqueous solution and non-aqueous solvents. This complex exhibits large fluorescence enhancement after binding with G-quadruplex DNA, and displays good fluorescent selectivity over other DNAs. The limit of detection is 6 nm for 22AG in Na⁺ and 43 nm for 22AG in K⁺, respectively. The results demonstrated that nitro-substituted ruthenium (II) complexes can be utilized to design as G-quadruplex fluorescent probes by protection of the nitro group on the complex from water.     

Antioxidant Activity of Ruthenium Cyclopentadienyl Complexes Bearing Succinimidato and Phthalimidato Ligands

In these studies, we investigated the antioxidant activity of three ruthenium cyclopentadienyl complexes bearing different imidato ligands: (η⁵-cyclopentadienyl)Ru(CO)₂-N-methoxysuccinimidato (1), (η⁵-cyclopentadienyl)Ru(CO)₂-N-ethoxysuccinimidato (2), and (η⁵-cyclopentadienyl)Ru(CO)₂-N-phthalimidato (3). We studied the effects of ruthenium complexes 1–3 at a low concentration of 50 µM on the viability and the cell cycle of peripheral blood mononuclear cells (PBMCs) and HL-60 leukemic cells exposed to oxidative stress induced by hydrogen peroxide (H₂O₂). Moreover, we examined the influence of these complexes on DNA oxidative damage, the level of reactive oxygen species (ROS), and superoxide dismutase (SOD) activity. We have observed that ruthenium complexes 1–3 increase the viability of both normal and cancer cells decreased by H₂O₂ and also alter the HL-60 cell cycle arrested by H₂O₂ in the sub-G1 phase. In addition, we have shown that ruthenium complexes reduce the levels of ROS and oxidative DNA damage in both cell types. They also restore SOD activity reduced by H₂O₂. Our results indicate that ruthenium complexes 1–3 bearing succinimidato and phthalimidato ligands have antioxidant activity without cytotoxic effect at low concentrations. For this reason, the ruthenium complexes studied by us should be considered interesting molecules with clinical potential that require further detailed research.     

Synthesis, characterization and DNA-binding studies of ruthenium(II) mixed-ligand complexes containing dipyrido[1,2,5]oxadiazolo[3,4-b]quinoxaline

A novel ligand dipyrido[1,2,5]oxadiazolo[3,4-b]quinoxaline (dpoq) and its complexes [Ru(bpy)₂(dpoq)]²⁺ and [Ru(phen)₂(dpoq)]²⁺ (bpy = 2,2′-bipyridine; phen = 1,10-phenanthroline) have been synthesized and characterized by elemental analysis, electrospray mass spectra and ¹H NMR. The interaction of Ru(II) complexes with calf thymus DNA (CT-DNA) was investigated by absorption spectroscopy, fluorescence spectroscopy, thermal denaturation and viscosity measurements. Results suggest that two Ru(II) complexes bind to DNA via an intercalative mode.     

Synthesis and DNA interaction studies of ruthenium(II) complexes with isatino[1, 2-b]-1,4,8,9-tetraazatriphenylene as an intercalative ligand

The binding of the ruthenium(II) complexes [Ru(bpy)₂(ITAP)](ClO₄)₂ (bpy = 2,2’-bipyridine) and [Ru(phen)₂(ITAP)](ClO₄)₂ (phen = 1,10-phenanthroline, ITAP = isatino[1,2-b]-1,4,8,9-tetraazatriphenylene) to calf thymus DNA (CT-DNA) have been investigated with UV–visible and emission spectroscopy, viscosity measurements, thermal denaturation, and photoactivated cleavage. The experimental results indicate that the two complexes bind to CT-DNA through an intercalative mode. The two Ru(II) complexes in the presence of plasmid pBR322 DNA have been found to give rise to nicking of DNA upon irradiation.     

Synthesis, characterization and photophysics of bimetallic manganese(I) and ruthenium(II) complexes

A series of new manganese(I) and ruthenium(II) monometallic and bimetallic complexes made of 2,2′-bipyridine and 1,10-phenanthroline ligands, [Mn(CO)₃(NN)(4,4′-bpy)]⁺, [{(CO)₃(NN)Mn}₂(4,4′-bpy)]²⁺ and [(CO)₃(NN)Mn(4,4′-bpy)Ru(NN)₂Cl]²⁺ (NN = 2,2′-bipyridine, 1,10-phenanthroline; 4,4′-bpy = 4,4′-bipyridine) are synthesized and characterized, in addition to already known ruthenium(II) complexes [Ru(NN)₂Cl(4,4′-bpy)]⁺ and [Cl(NN)₂Ru(4,4′-bpy)Ru(NN)₂Cl]²⁺. The electrochemical properties show that there is a weak interaction between two metal centers in Mn–Ru heterobimetallic complexes. The photophysical behavior of all the complexes is studied. The Mn(I) monometallic and homobimetallic complexes have no detectable emission. In Mn–Ru heterobimetallic complexes, the attachment of Mn(I) with Ru(II) provides interesting photophysical properties.     

Rationally designed Ru(ii)-metallacycle chemo-phototheranostic that emits beyond 1000 nm

Ruthenium complexes are emerging as potential complements to platinum drugs. They also show promise as photo-diagnostic and therapeutic agents. However, most ruthenium species studied to date as potential drugs are characterized by short excitation/emission wavelengths. This limits their applicability for deep-tissue fluorescence imaging and light-based therapeutic treatments. Here, we report a Ru(ii) metallacycle (Ru1100) that emits at ≥1000 nm. This system possesses excellent deep-tissue penetration capability (∼7 mm) and displays good chemo-phototherapeutic performance. In vitro studies revealed that Ru1100 benefits from good cellular uptake and produces a strong anticancer response against several cancer cell lines, including a cisplatin-resistant A549 cell line (IC₅₀ = 1.6 μM vs. 51.4 μM for cisplatin). On the basis of in vitro studies, it is concluded that Ru1100 exerts its anticancer action by regulating cell cycle progression and triggering cancer cell apoptosis. In vivo studies involving the use of a nanoparticle formulation served to confirm that Ru1100 allows for high-performance NIR-II fluorescence imaging-guided precise chemo-phototherapy in the case of A549 tumour mouse xenografts with no obvious side effects. This work thus provides a paradigm for the development of long-wavelength emissive supramolecular theranostic agents based on ruthenium.

Along-wavelength emissive Ru(ii) metallacycle chemo-phototheranostic was prepared via self-assembly that exhibits excellent photostability, deep-tissue penetration capability, and promising chemo-phototherapeutic performance in vitro and in vivo.     

Synthesis and α-Glucosidase Inhibition Activity of 2-[3-(Benzoyl/4-bromobenzoyl)-4-hydroxy-1,1-dioxido-2H-benzo[e][1,2]thiazin-2-yl]-N-arylacetamides: An In Silico and Biochemical Approach

Diabetes mellitus (DM) is a chronic disorder and has affected a large number of people worldwide. Insufficient insulin production causes an increase in blood glucose level that results in DM. To lower the blood glucose level, various drugs are employed that block the activity of the α-glucosidase enzyme, which is considered responsible for the breakdown of polysaccharides into monosaccharides leading to an increase in the intestinal blood glucose level. We have synthesized novel 2-(3-(benzoyl/4-bromobenzoyl)-4-hydroxy-1,1-dioxido-2H-benzo[e][1,2]thiazin-2-yl)-N-arylacetamides and have screened them for their in silico and in vitro α-glucosidase inhibition activity. The derivatives 11c, 12a, 12d, 12e, and 12g emerged as potent inhibitors of the α-glucosidase enzyme. These compounds exhibited good docking scores and excellent binding interactions with the selected residues (Asp203, Asp542, Asp327, His600, Arg526) during in silico screening. Similarly, these compounds also showed good in vitro α-glucosidase inhibitions with IC₅₀ values of 30.65, 18.25, 20.76, 35.14, and 24.24 μM, respectively, which were better than the standard drug, acarbose (IC₅₀ = 58.8 μM). Furthermore, a good agreement was observed between in silico and in vitro modes of study.     

DNA-Binding Capabilities and Anticancer Activities of Ruthenium(II) Cymene Complexes with (Poly)cyclic Aromatic Diamine Ligands

Ruthenium(II) arene complexes of the general formula [RuCl(η⁶-p-cymene)(diamine)]PF₆ (diamine = 1,2-diaminobenzene (1), 2,3-diaminonaphthalene (2), 9,10-diaminophenanthrene (3), 2,3-diaminophenazine (4), and 1,2-diaminoanthraquinone (5) were synthesized. Chloro/aqua exchange was evaluated experimentally for complexes 1 and 2. The exchange process was investigated theoretically for all complexes, revealing relatively fast exchange with no significant influence from the polycyclic aromatic diamines. The calf thymus DNA (CT-DNA) binding of the complexes increased dramatically upon extending the aromatic component of the diamines, as evaluated by changes in absorption spectra upon titration with different concentrations of CT-DNA. An intercalation binding mode was established for the complexes using the increase in the relative viscosity of the CT-DNA following addition of complexes 1 and 2. Theoretical studies showed strong preference for replacement of water by guanine for all the complexes, and relatively strong Ru–N_guanine bonds. The plane of the aromatic systems can assume angles that support non-classical interactions with the DNA and covalent binding, leading to higher binding affinities. The ruthenium arenes illustrated in this study have promising anticancer activities, with the half maximal inhibitory concentration (IC₅₀) values comparable to or better than cisplatin against three cell lines.     

Biocatalytic cascades and intercommunicated biocatalytic cascades in microcapsule systems

Biomolecule-loaded nucleic acid-functionalized carboxymethyl cellulose hydrogel-stabilized microcapsules (diameter ca. 2 μm) are introduced as cell-like containments. The microcapsules are loaded with two DNA tetrahedra, T₁ and T₂, functionalized with guanosine-rich G-quadruplex subunits, and/or with native enzymes (glucose oxidase, GOx, and/or β-galactosidase, β-gal). In the presence of K⁺-ions and hemin, the T₁/T₂ tetrahedra constituents, loaded in the microcapsules, assemble into a hemin/G-quadruplex bridged tetrahedra dimer DNAzyme catalyzing the oxidation of Amplex Red to Resorufin by generating H₂O₂. In the presence of co-loaded GOx or GOx/β-gal, the GOx//T₁/T₂ hemin/G-quadruplex cascade catalyzing the glucose-mediated oxidation of Amplex Red to Resorufin, and the three-biocatalysts cascade consisting of β-gal//GOx//hemin/G-quadruplex bridged T₁/T₂ catalyzing the lactose-driven oxidation of Amplex Red to Resorufin proceed in the microcapsules. Enhanced biocatalytic transformations in the microcapsules, as compared to the performance of the reactions in a homogeneous phase, are observed, due to the proximity of the biocatalysts in a confined volume. As the synthetic methodology to prepare the microcapsules yields boundaries functionalized with complementary nucleic acid tethers, the dynamic association of different microcapsules, loaded selectively with biomolecular catalysts, proceeds. The dynamic dimerization of GOx-loaded microcapsules and hemin/G-quadruplex bridged T₁/T₂ DNAzyme-loaded microcapsules yields effective intercommunicated microcapsules driving the GOx//hemin/G-quadruplex bridged T₁/T₂ DNAzyme cascade. In addition, the dynamic dimerization of GOx-loaded microcapsules with β-gal//hemin/G-quadruplex bridged T₁/T₂-loaded microcapsules enables the bi-directional intercommunicated operation of the lactose-stimulated three catalysts β-gal//GOx//hemin/G-quadruplex bridged T₁/T₂ DNAzyme cascade. The guided separation and formation of dynamic supramolecular dimer microcapsular containments, and the dictated switchable operation of intercommunicated biocatalytic cascades are demonstrated.

Dynamic dimerization of GOx-loaded microcapsules with β-gal//hemin/G-quadruplex-bridged T₁/T₂-loaded microcapsules guides the bi-directional intercommunication of the three catalysts cascade.     

Actinide arene-metalates: ion pairing effects on the electronic structure of unsupported uranium–arenide sandwich complexes

Addition of [UI₂(THF)₃(μ-OMe)]₂·THF (2·THF) to THF solutions containing 6 equiv. of K[C₁₄H₁₀] generates the heteroleptic dimeric complexes [K(18-crown-6)(THF)₂]₂[U(η⁶-C₁₄H₁₀)(η⁴-C₁₄H₁₀)(μ-OMe)]₂·4THF (118C6·4THF) and {[K(THF)₃][U(η⁶-C₁₄H₁₀)(η⁴-C₁₄H₁₀)(μ-OMe)]}₂ (1THF) upon crystallization of the products in THF in the presence or absence of 18-crown-6, respectively. Both 118C6·4THF and 1THF are thermally stable in the solid-state at room temperature; however, after crystallization, they become insoluble in THF or DME solutions and instead gradually decompose upon standing. X-ray diffraction analysis reveals 118C6·4THF and 1THF to be structurally similar, possessing uranium centres sandwiched between bent anthracenide ligands of mixed tetrahapto and hexahapto ligation modes. Yet, the two complexes are distinguished by the close contact potassium-arenide ion pairing that is seen in 1THF but absent in 118C6·4THF, which is observed to have a significant effect on the electronic characteristics of the two complexes. Structural analysis, SQUID magnetometry data, XANES spectral characterization, and computational analyses are generally consistent with U(iv) formal assignments for the metal centres in both 118C6·4THF and 1THF, though noticeable differences are detected between the two species. For instance, the effective magnetic moment of 1THF (3.74 μ_B) is significantly lower than that of 118C6·4THF (4.40 μ_B) at 300 K. Furthermore, the XANES data shows the U L_III-edge absorption energy for 1THF to be 0.9 eV higher than that of 118C6·4THF, suggestive of more oxidized metal centres in the former. Of note, CASSCF calculations on the model complex {[U(η⁶-C₁₄H₁₀)(η⁴-C₁₄H₁₀)(μ-OMe)]₂}²⁻ (1*) shows highly polarized uranium–arenide interactions defined by π-type bonds where the metal contributions are primarily comprised by the 6d-orbitals (7.3 ± 0.6%) with minor participation from the 5f-orbitals (1.5 ± 0.5%). These unique complexes provide new insights into actinide–arenide bonding interactions and show the sensitivity of the electronic structures of the uranium atoms to coordination sphere effects.

Use of Chatt metal-arene protocols with uranium leads to the synthesis of the first well-characterized, unsupported actinide–arenide sandwich complexes. The electronic structures of the actinide centres show a key sensitivity to ion pairing effects.     

DNA interactions of ruthenium(II) complexes with a polypyridyl ligand: 2-(2, 5-dimethoxyphenyl)-1<Emphasis Type="Italic">H</Emphasis>-imidazo[4,5-<Emphasis Type="Italic">f</Emphasis>]1,10-phenanthroline

This article describes the synthesis of a polypyridyl ligand, namely 2-(2, 5-dimethoxyphenyl)-1H-imidazo[4,5-f]1,10-phenanthroline (DMPIP) and its Ru(II) complexes, namely [Ru(bipy)₂DMPIP]²⁺ (1), [Ru(dmb)₂DMPIP]²⁺ (2) and [Ru(phen)₂DMPIP]²⁺ (3) ((bipy = 2,2′-bipyridine, dmb = 4,4′-dimethyl-2,2′-bipyridine, phen = 1,10-phenanthroline). The complexes were characterized by elemental analysis, plus IR, ¹H-NMR and ¹³C [¹H]-NMR spectra. The interactions of the complexes with calf thymus DNA were investigated. The results indicate that the three complexes can intercalate into DNA. Under irradiation at 365 nm, all three complexes promote the photocleavage of plasmid pBR 322 DNA. Inhibitor studies suggest that singlet oxygen plays a significant role in the cleavage mechanism for the complexes.