Five new mononuclear ruthenium(II) tris-ligated complexes have been synthesised, varying through the choice of azine in the family of 3-azinyl-4-(4-methylphenyl)-5-phenyl-4H-1,2,4-triazole ligands (Lazine): [Ru(Lpyridine)](PF6)2 (1), [Ru(Lpyridazine)](PF6)2 (2), [Ru(L4-pyrimidine)](PF6)2 (3), [Ru(Lpyrazine)](PF6)2 (4), [Ru(L2-pyrimidine)](PF6)2 (5). Three of them, 1·2MeCN·Et2O, 3·2MeCN·Et2O and 4·2MeCN, have been structurally characterised, confirming the presence of the meridional isomer, as was previously reported for the FeII analogues. Cyclic voltammetry studies, in dry CH3CN vs. Ag/0.01 M AgNO3, show that all five RuII complexes undergo a reversible RuIII/RuII process, with the midpoint potential (Em) increasing from 0.87 to 1.18 V as the azine is changed: pyridine < pyridazine < 2-pyrimidine < 4-pyrimidine < pyrazine. A strong inverse linear correlation (R2 = 0.98) is found between the RuIII/RuII redox potential and the calculated HOMO orbital energies, which is consistent with the expectation that it is easier to oxidise (lower Em) a metal ion with a higher HOMO orbital energy. The same trend was reported earlier for the family of analogous FeII complexes, albeit at lower values of Em in all cases. In addition, the ionisation potentials of the RuII complexes, as well as those of the other group 8 analogues (FeII and OsII), showed a linear relationship with Epa. As the MIII/II redox potentials of a family of complexes has been previously reported to correlate with ligand pKa values, a computational protocol to calculate, in silico, the pKa of the Lazine family of ligands was developed. A strong linear relationship was found between the readily calculated pKa of the Lazine ligand and the Epa of the MII complex, for all three families of complexes (R2 = 0.98).

The rational design of earth-abundant and efficient electrocatalysts to replace precious metal-based materials is highly anticipated for overall water splitting. Herein, NiCo2O4 electrocatalysts with different Fe doping amounts (Fex-NCO, x = 1, 2, 3) were synthesized by a low-temperature chemical method. It was interesting to find that the doping of Fe induced the formation of NiCo2O4 nanotube arrays by modulating the Fe content. The Fe3-NCO electrode with a nanotube structure and rich oxygen vacancies exhibited exceptional electrocatalytic activities for the hydrogen evolution reaction (97 mV, 10 mA cm−2) and oxygen evolution reaction (188.4 mV, 10 mA cm−2). DFT calculations revealed that Fe promoted the modulation of the electronic structure, which played a crucial role in optimizing the reaction intermediates and altered the energy level of the d band center, and as a result, enhanced the water dissociation ability. Additionally, a low cell voltage of 1.56 V (10 mA cm−2) was realized for water splitting based on an as-fabricated Fe-doped NiCo2O4 nanotube array bifunctional electrode.

Four heteroanionic oxyhalides, CeClMoO4, CeBrMoO4, CeClWO4, and CeBrWO4, have been studied as multifunctional materials, which show a combination of good second harmonic generation (SHG) response and photocurrent signals. Millimeter-sized CeHaVIO4 (Ha = Cl, Br; VI = Mo, W) crystals were grown by halide salt flux. The crystal structure of CeHaVIO4 crystals was accurately determined by single-crystal X-ray diffraction. CeClMoO4, CeBrMoO4, and CeBrWO4 are isostructural to each other, and crystallize in the acentric LaBrMoO4 structure type. CeClWO4 crystallizes in a new structure type with unit cell parameters of a = 19.6059(2) Å, b = 5.89450(10) Å, c = 7.80090(10) Å, and β = 101.4746(8)°. The bandgaps of CeHaVIO4 fall into the range of 2.8(1)–3.1(1) eV, which are much smaller than those of isotypic LaHaVIO4 (Ha = Cl, Br; VI = Mo, W) in the range of 3.9(1)–4.3(1) eV. The narrowing of bandgaps in CeHaVIO4 originates from the presence of partially filled 4f orbitals of cerium atoms, which was confirmed by density functional theory (DFT) calculations. The moderate bandgaps make CeHaVIO4 suitable for infrared nonlinear optical (IR NLO) applications. CeBrMoO4 and CeBrWO4 exhibit moderate SHG responses of 0.58× AGS and 0.46× AGS, respectively, and are both type-I phase-matching materials. Moderate SHG response, easy growth of crystals, high ambient stability, and type-I phase-matching behavior make CeBrMoO4 and CeBrWO4 great materials for IR NLO applications. CeHaVIO4 films also exhibited good photocurrent response upon light radiation. This work demonstrates the rich structural chemistry of the REHaVIO4 (RE = Y, La–Lu; Ha = Cl, Br; VI = Mo, W) family and the potential presence of more multifunctional materials.

The rich coordination chemistry of lanthanoid ions (Ln3+) is currently exploited in a vast and continuously expanding array of applications. Chelating agents are central in the development of Ln3+-complexes and in tuning their physical and chemical properties. Most chelators for Ln3+-complexation are derived from the macrocyclic DOTA or from linear DTPA platforms, both of which arise from fossil-based starting materials. Herein, we report a green and efficient approach to a chelating agent (EHDTA), derived from cheap and largely available furfurylamine. The oxygenated heterocycle of the latter is converted to a stereochemically defined and rigid heptadentate chelator, which shows good affinity towards Ln3+ ions. A combination of NMR, relaxometric, potentiometric and spectrophotometric techniques allows us to shed light on the interesting coordination chemistry of Ln3+–EHDTA complexes, unveiling a promising ligand for the chelation of this important family of metal ions.

Single crystals of two new intermetallic phases Sm2Mn1−xGa6−yGey (x = 0.1–0.3, y = 0.6–1.0) and Sm4MnGa12−yGey (y = 3.0–3.5) were grown using a self-flux technique. According to single crystal X-ray diffraction data, Sm4MnGa12−yGey is characterised by the Y4PdGa12 structure type (a ∼ 8.65 Å; Imm), while Sm2Mn1−xGa6−yGey formally adopts the K2PtCl6 structure type (a ∼ 8.71 Å; Fmm). The general features of both compounds with rather similar crystal structures are represented by the alternation of empty and Mn-filled p-element octahedra, the order of which is determined by the Mn concentration. The diffraction data for Sm2Mn1−xGa6−yGey reveal a large concentration of Mn vacancies (x ∼ 0.3), which affects adjacent Ga/Ge atoms leading to their shift towards the vacancy. Both compounds demonstrate two ferromagnetic-like transitions and the presence of two interacting Mn and Sm magnetic sublattices. The Mn sublattice orders at TC1 of 143 K and 318 K, while the Sm one orders at lower temperatures at TC2 of 50 K and 280 K for Sm4MnGa8.6Ge3.4 and Sm2Mn0.74Ga5.1Ge0.9, respectively. The increase in Mn content not only increases the ordering temperatures, but also dramatically decreases the coercivity μ0HC from 230 mT to just 6.5 mT at 2 K. Despite the presence of two magnetically active sublattices in Sm2Mn0.74Ga5.1Ge0.9, the magnetic entropy change is quite low and only reaches 0.3 J kg−1 K−1 at T = 300 K and μ0H = 5 T, while the estimated relative cooling power (RCP) is about 36 J kg−1 at 5 T.

The development of low-cost earth-abundant electrocatalysts to produce ammonia (NH3) with high efficiency for the nitrogen (N2) reduction reaction (NRR) remains challenging. Herein, we propose the development of highly efficient ultrathin nitrogen-vacancy-rich molybdenum nitride nanosheets (MoN-NV) for NRR using basic electrolytes under ambient conditions. In 0.1 M KOH, this catalyst attained a high faradaic efficiency (FE) of ∼14% with an NH3 yield of 22.5 μg h−1 mg−1cat at −0.3 V vs. a reversible hydrogen electrode under ambient conditions. The characterization results and electrochemical studies disclosed that nitrogen vacancies in the MoN-NV nanosheets played a critical role in the enhanced electrocatalytic activity for NRR. Furthermore, the recycling tests confirmed the stability of the catalyst during NRR electrolysis.

Crystallographic investigations of eight homoleptic N,N′-dimethylpropyleneurea (dmpu) coordinated metal ions in the solid state, [Mg(dmpu)5]I2 (1), [Ca(dmpu)6]I2 (2), [Ca(dmpu)6](ClO4)2 (3), [Ca(dmpu)6](CF3SO3)2 (4), [Sr(dmpu)6](CF3SO3)2 (5), [Ba(dmpu)6](CF3SO3)2 (6), [Sc(dmpu)6]I3 (7), and [Pr(dmpu)6]I(I3)2 (8), and the complex [CoBr2(dmpu)2] (9) as well as the structures of the dmpu coordinated calcium, strontium, barium, scandium(III) and cobalt(II) ions and the cobalt(II) bromide complex in dmpu solution as determined by EXAFS are reported. The methyl groups in the dmpu molecule are close to the oxygen donor atom, causing steric restrictions, and making dmpu space-demanding at coordination to metal ions. The large volume required by the dmpu ligand at coordination contributes to crowdedness around the metal ion with often lower coordination numbers than for oxygen donor ligands without such steric restrictions. The crowdedness is seen in M⋯H distances equal to or close to the sum of the van der Waals radii. To counteract the space-demand at coordination, the dmpu molecule has an unusual ability to increase the M–O–C bond angle to facilitate as large coordination numbers as possible. M–O–C bond angles in the range of 125–170° are reported depending on the crowdedness caused by the coordination figure and the M–O bond distance. All reported structures of dmpu coordinated metal ions in both the solid state and dmpu solution are summarized to study the relationship between the M–O–C bond angle and the crowdedness around the metal ion. However, highly symmetric complexes seem to be favoured in the solid state due to favourable lattice energies. As a result, the dmpu coordinated lanthanoid(III) ions are octahedral in the solid state, while they, except lutetium, are seven-coordinate in the dmpu solution.

Nowadays, the poor conductivity and unstable structure have become obstacles for the popularization of Na3V2(PO4)3 (NVP). In the current work, a dual-modified Mn0.1Cl0.3-NVP composite doped with Mn and Cl is prepared by a facile sol–gel method. When Mn2+ with a large ionic radius replaces small V3+, it can improve the stability of the NVP crystal structure. In addition, the replacement of V3+ by Mn2+ in a low valence state can generate redundant hole carriers, which is conducive to the rapid transport of electrons. The substitution of PO43− by Cl−, which is more electronegative, can reduce the impedance and facilitate the movement of Na+. Owing to the synergistic effect of Mn and Cl co-substitution, the structural stability of NVP was systematically enhanced, and the electron transfer and ion diffusion were effectively improved. Consequently, the optimized Mn0.1Cl0.3-NVP sample demonstrated superior electrochemical performance and kinetic properties. It exhibited a high reversible capacity of 109.2 mA h g−1 at 0.1C. Even at 15 and 30C, high discharge capacities of 70.3 mA h g−1 and 68.2 mA h g−1 were observed after 2000 cycles with capacity retention above 80%. Moreover, it delivered remarkable capacities of 77.1 and 73.4 mA h g−1 at 100 and 200C with retained capacity values of 50.3 and 47 mA h g−1, respectively, after 2000 cycles. Furthermore, the assembled Mn0.1Cl0.3-NVP//HC full cell delivered a high value of 94.7 mA h g−1 and lit LED bulbs, indicating its excellent application potential.

We herein report the synthesis and catalytic application of a new family of dinuclear Cu(I) complexes based on [N,P]-pyrrole ligands. The Cu(I) complexes (4a–d) were obtained in good yields and their catalytic properties were evaluated in the1,3-dipolar cycloaddition of azomethine ylides and electron-deficient alkenes. The air-stable complexes 4a–d exhibited high endo-diasteroselectivity to obtain substituted pyrrolidines, and the catalytic system showed excellent reactivity and wide substitution tolerance.

With increasing interest in nickel-based electrocatalysts, three heteroleptic Ni(II) dithiolate complexes with the general formula [Ni(II)L(L′)2] (1–3), L = 2-(methylene-1,1′-dithiolato)-5,5′-dimethylcyclohexane-1,3-dione and L′ = triphenylphosphine (1), 1,1′-bis(diphenylphosphino)ferrocene (DPPF) (2), and 1,2-bis(diphenylphosphino)ethane (DPPE) (3), have been synthesized and characterized by various spectroscopic techniques (UV-vis, IR, 1H, and 31P{1H} NMR) as well as the electrochemical method. The molecular structure of complex 2 has also been determined by single-crystal X-ray crystallography. The crystal structure of complex 2 reveals a distorted square planar geometry around the nickel metal ion with a NiP2S2 core. The cyclic voltammograms reveal a small difference in the redox properties of complexes (ΔE° = 130 mV) while the difference in the catalytic half-wave potential becomes substantial (ΔEcat/2 = 670 mV) in the presence of 15 mM CF3COOH. The common S^S-dithiolate ligand provides stability, while the rigidity effect of other ligands (DPPE (3) > DPPF (2) > PPh3 (1)) regulates the formation of the transition state, resulting in the NiIII–H intermediate in the order of 1 > 2 > 3. The foot-of-the-wave analysis supports the widely accepted ECEC mechanism for Ni-based complexes with the first protonation step as a rate-determining step. The electrocatalytic proton reduction activity follows in the order of complex 1 > 2 > 3. The comparatively lower overpotential and higher turnover frequency of complex 1 are attributed to the flexibility of the PPh3 ligand, which favours the easy formation of a transition state.

Chiral nickel complexes containing NHC-carboxylate chelate ligands derived from the (S)-isomeric form of amino acids have been synthesised from the corresponding imidazolium salt and nickelocene. The presence of the carboxylate on the N-side arm of the heterocycle results in the competing formation of mixtures of mono- and bis-NHC complexes (i.e., [Ni(η5-Cp)(κ2-C,O-NHC)] and [Ni(κ2-C,O-NHC)2]), both of which retain the (S)-configuration of the stereogenic center and which can be separated by chromatography. Both the 18e− and 16e− complexes are found to be very stable and cannot be interconverted. The composition of the resulting mixtures depends mainly on the entity of the amino acid residue and, of more practical interest, on the reaction conditions. Thus, microwave heating and MeCN as a solvent favor the formation of the half-sandwich nickel complexes, rather than the bis-NHC compounds. Some of the [Ni(η5-Cp)(κ2-C,O-NHC)] complexes turn out to be among the best nickel catalysts for the hydrosilylative reduction of p-acetophenones described to date, although without chiral induction, in the absence of activating additives and under mild catalytic conditions.

In the present work, copper whitlockite (Cu-WH, Ca18Cu2(HPO4)2(PO4)12) was successfully synthesized and comprehensively characterized, founding the base knowledge for its future studies in medicine, particularly for bone regeneration. This material is a copper-containing analog of the well-known biomineral magnesium whitlockite (Mg-WH, Ca18Mg2(HPO4)2(PO4)12). The synthesis of powders was performed by a dissolution–precipitation method in an aqueous medium under hydrothermal conditions. Phase conversion from brushite (CaHPO4·2H2O) to Cu-WH took place in an acidic medium in the presence of Cu2+ ions. Optimization of the synthesis conditions in terms of medium pH, temperature, time, Ca/Cu molar ratio and concentration of starting materials was performed. The crystal structure of the synthesized products was confirmed by XRD, FTIR and Raman spectroscopy, 1H and 31P solid-state NMR, and EPR. Morphological features and elemental distribution of the synthesized powders were studied by means of SEM/EDX analysis. The ion release in SBF solution was estimated using ICP-OES. Cytotoxicity experiments were performed with MC3T3-E1 cells. The study on thermal stability revealed that the synthesized material is thermally unstable and gradually decomposes upon annealing to Cu-substituted β-Ca3(PO4)2 and Ca2P2O7.

A graphical abstract is available for this content

A suitable drug delivery strategy for metallodrugs is as significant as the strategies adopted for an efficient metallodrug design. In this study, piperlongumine, which is isolated from long pepper, is coordinated with a Ru(II)-p-cymene moiety to obtain an organoruthenated complex containing the natural product (Ru(pip)). The isolated complex shows higher cytotoxicity in MCF-7 breast cancer cells than in THP-1 leukemia and HepG2 liver cancer cells. The IC50 value of the complex in non-cancerous HEK-239 cells is also almost equal to that in MCF-7 cells. Next, with an aim to modulate the antiproliferative activity of Ru(pip) using a drug delivery strategy, the complex is loaded into mesoporous silica nanorods (MSNRs), which have a higher surface area than spherical silica nanoparticles. Furthermore, the outer surface of the loaded nanorods is covered with a polydiacetylene-lipid (PL) hybrid bilayer. Given the unique optical properties of polydiacetylene, the PL coating modifies non-fluorescent MSNRs into red-emissive particles (PL-Ru(pip)@MSNRs), which can be useful for diagnostic applications. The release profile studies reveal that the ene-yne conjugation in the PL coating ensures the sustained release of the complex from nanoparticles in both physiological and simulated cancer cell media. While Ru(pip) exhibits both necrotic and apoptotic modes of cell death, PL-Ru(pip)@MSNRs preferably induce the apoptotic mode of cell death in MCF-7 and THP-1 cells. Also, the nanoformulation exhibits a higher percentage of cell cycle arrest in the G0/G1 phase than Ru(pip), as measured by flow cytometry analysis. In contrast, the in vitro antioxidant potency of the complex is decreased after being loaded into PL-coated silica nanoparticles.

A novel phosphate containing barium, cobalt, and iron was synthesized in single-crystal and polycrystalline forms. Single crystal-based X-ray measurements revealed that it crystallizes in the monoclinic system with the P21/c space group. The structure is made up of linkages between FeO6 octahedra, CoO4 square planar units, CoO5 square pyramidal units, and PO4 tetrahedra through edges and/or vertices. The interconnection of these polyhedra leads to a three-dimensional framework with tunnels along the a-axis where the Ba2+ cations are located. The polycrystalline form was prepared via the sol–gel method and its XRD pattern was refined by the Le Bail method. Morphological and elemental mapping analyses of this phosphate were performed by scanning electron microscopy. In addition, infrared and Raman spectroscopy provided more insights into chemical bonding. The magnetic behavior was antiferromagnetic below TN ∼ 20 K. Optical measurements revealed a direct bandgap with an energy Eg of 2.83 eV.

Designing wide-bandgap chalcogenides is one of the most important ways of obtaining high-performance infrared (IR) functional materials. In this work, two Mg-based metal thiophosphates, namely Na6Mg3P4S16 (NMPS) and RbMg2PS4Cl2 (RMPSC), were successfully obtained by introducing [MgS6] and [MgSxCl6−x] octahedra into thiophosphates. In addition, their crystal structures were determined, a first for Mg-containing [PS4]-based thiophosphates to the best of our knowledge. Their bandgaps were investigated in theoretical ways and verified by taking experimental measurements, and determined to be 3.80 eV for NMPS and 3.93 eV for RMPSC, values greater than those of the other investigated thiophosphate halides. The wide bandgaps of NMPS and RMPSC were attributed, based on theoretical calculations, to the [MgSxCl6−x] (x = 0–6) octahedron.

A comprehensive density functional theory investigation has been presented towards the comparison of the C–H activation reactivity between high-valent iron-oxo and ruthenium-oxo complexes. A total of four compounds, e.g., [Ru(IV)O(tpy-dcbpy)] (1), [Fe(IV)O(tpy-dcbpy)] (1′), [Ru(IV)O(TMCS)] (2), and [Fe(IV)O(TMCS)] (2′), have been considered for this investigation. The macrocyclic ligand framework tpy(dcbpy) implies tpy = 2,2′:6′,2′′-terpyridine, dcbpy = 5,5′-dicarboxy-2,2′-bipyridine, and TMCS is TMC with an axially tethered –SCH2CH2 group. Compounds 1 and 2′ are experimentally synthesized standard complexes with Ru and Fe, whereas compounds 1′ and 2 were considered to keep the macrocycle intact when switching the central metal atom. Three reactants including benzyl alcohol, ethyl benzene, and dihydroanthracene were selected as substrates for C–H activation. It is noteworthy to mention that Fe(IV)O complexes exhibit higher reactivity than those of their Ru(IV)O counterparts. Furthermore, regardless of the central metal, the complex featuring a tpy-dcbpy macrocycle demonstrates higher reactivity than that of TMCS. Here, a thorough analysis of the reactivity-controlling characteristics—such as spin state, steric factor, distortion energy, energy of the electron acceptor orbital, and quantum mechanical tunneling—was conducted. Fe(IV)O exhibits the exchanged enhanced two-state-reactivity with the quintet reactive state, whereas Ru(IV)O has only a triplet reactive state. Both the distortion energy and acceptor orbital energy are low in the case of Fe(IV)O supporting its higher reactivity. All the investigated C–H activation processes involve a significant contribution from hydrogen tunneling, which is more pronounced in the case of Ru, although it cannot alter the reactivity pattern. Furthermore, it has also been found that, independent of the central metal, aliphatic hydroxylation is always preferable to aromatic hydroxylation. Overall, this work is successful in establishing and investigating the cause of enzymes’ natural preference for Fe over Ru as a cofactor for C–H activation enzymes.

A graphical abstract is available for this content

We present an approach for connecting the magnetic anisotropy of lanthanide mononuclear complexes with their f-orbital splitting for both idealized and real coordination environments. Our proposal is straightforward to apply and provides sensible estimations of the energy spacing of the ground multiplet for axial magnetic systems. This energy splitting controls Single-Molecule Magnet properties of lanthanide complexes, determining key parameters such as the demagnetization energy barrier (Ueff). Importantly, this approach is consistent with the current paradigm of oblate and prolate preferences for the distribution of the f-electron density, but delivers a finer description for ions belonging to the same group (e.g. the oblates TbIII and DyIII). The model provides simple explanations for some general trends observed experimentally (e.g. the low barriers for ErIII complexes in comparison to DyIII or the large barriers observed for cyclopentadienyl DyIII complexes in comparison with other ligands based on organometallic rings), contributing as a valuable tool to expand our description of ligand field effects in lanthanide-based SMMs.

The marine natural product norzooanemonin (1,3-dimethylimidazolium-4-carboxylate) has been used to prepare a series of carboxyl- or carboxylate-functionalized N-heterocyclic carbene (NHC) gold(I) complexes from [(Me2S)AuCl] in the presence of potassium carbonate. The potential of the resulting mono- and dicarbene complexes to act as cytotoxic or antibacterial drugs was investigated.