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Nickel is an important element utilized in various industrial/metallurgical processes, such as surgical and dental prostheses, Ni-Cd batteries, paint pigments, electroplating, ceramics, computer magnetic tapes, catalysis, and alloy manufacturing. However, its extensive use and associated waste production have led to increased nickel pollution in soils and water bodies, which adversely affects human health, animals and plants. This issue has prompted researchers to develop various optical probes, hereafter luminescent/colorimetric sensors, for the facile, sensitive and selective detection of nickel, particularly in biological and environmental contexts. In recent years, numerous functionalized chemosensors have been reported for imaging Ni2+, both in vivo and in vitro. In this context, metal-based receptors offer clear advantages over conventional organic sensors (viz., organic ligands, polymers, and membranes) in terms of cost, durability, stability, water solubility, recyclability, chemical flexibility and scope. This review highlights recent advancements in the design and fabrication of hybrid receptors (i.e., metal complexes and MOFs) for the specific detection of Ni2+ ions in complex environmental and biological mixtures. [ABSTRACT FROM AUTHOR]

Intercalation compounds represent a unique class of materials that can be anisotropic (1D and 2D-based topology) or isotropic (3D) through their guest/host superlattice repetitive organisation. Intercalation refers to the reversible introduction of guest species with variable natures into a crystalline host lattice. Different host lattice structures have been used for the preparation of intercalation compounds, and many examples are produced by exploiting the flexibility and the ability of 2D-based hosts to accommodate different guest species, ranging from ions to complex molecules. This reaction is then carried out to allow systematic control and fine tuning of the final properties of the derived compounds, thus allowing them to be used for various applications. This review mainly focuses on the recent applications of intercalation layered compounds (ILCs) based on layered clays, zirconium phosphates, layered double hydroxides and graphene as heterogeneous catalysts, for environmental and health purposes, aiming at collecting and discussing how intercalation processes can be exploited for the selected applications. [ABSTRACT FROM AUTHOR]

Four novel Co(II) coordination compounds 1–4 of the general formula [Co(Ln)2][Co(NCY)4]·mCH3CN (where Ln are tridentate ligands L1 = 2,6-bis(1-hexyl-1H-benzimidazol-2-yl)pyridine for 1 and 2; L2 = 2,6-bis(1-octyl-1H-benzimidazol-2-yl)pyridine for 3; L3 = 2,6-bis(1-dodecyl-1H-benzimidazol-2-yl)pyridine for 4, Y = O for 1, 3, and 4 and Y = S for 2; m = 0 for 1 and 3, m = 0.5 for 2 and m = 2 for 4) were prepared and characterised. The molecular structures of all four compounds consist of the hexacoordinate complex cation [Co(Ln)2]2+ and tetracoordinate complex anion [Co(NCY)4]2−, with distorted octahedral and tetrahedral symmetry of coordination polyhedra, respectively. The electronic structures of all compounds feature an orbitally non-degenerate ground state well-separated from the lowest excited state, which allows the analysis of the magnetic anisotropy by the spin Hamiltonian model. ZFS parameters, derived from both CASSCF-NEVPT2 calculations and magnetic data analysis, indicate that tetrahedral anions [Co(NCY)4]2− exhibit small axial parameters ‖D‖ spanning the range of 2.2 to 7.7 cm−1, while octahedral cations [Co(Ln)2]2+ display significantly larger ‖D‖ parameters in the range of 37 to 95 cm−1. For 1–3, the Fourier-transform infrared magnetic spectroscopy (FIRMS) revealed a reasonable transmission with a magnetic absorption around the expected value for the ZFS accompanied by features allowing to identify phonon frequencies and simulate spin-phonon couplings. Dynamic magnetic investigations unveiled the field-induced slow relaxation of magnetisation, with maximal relaxation times (τ) of 92(2) μs for 2 at 2 K and BDC = 0.3 T. The temperature evolution of τ was analysed using a combination of Orbach, direct and Raman relaxations (Ueff = 8(1) K (5.6 cm−1)) or Orbach, direct and spin-phonon induced relaxations (Ueff = 10.3(9) K (7.2 cm−1)). The rest of the complexes, namely 1, 3, and 4 show field-induced slow relaxation of magnetisation with τ smaller than 16 μs. [ABSTRACT FROM AUTHOR]

In this work we report the synthesis, structural characterization and magnetic properties of a family of butterfly complexes {Cr2Ln2} with Ln = Tb (4), Ho (5), Er (6), Tm (7) and Yb (8), extending the family of previously reported isostructural compounds with Gd (1), Dy (2) and Y (3). As in 1 and 2, an anti-ferromagnetic Cr(III)–Ln(III) exchange interaction is found. For oblate ions 4 and 5, SMM behavior with a purely Orbach relaxation mechanism is observed with thermal barriers of 38 cm−1 (4) and 32 cm−1 (5). Complex 4 displays hysteresis opening up to 2.4 K with loss of magnetization at zero field. The prolate complex ions 6 and 7 are field-induced SMM's with dominant Orbach, direct and QTM relaxation mechanisms. Compound 8 did not show SMM properties. [ABSTRACT FROM AUTHOR]

A systematic study of the impact on the chemical reactivity of the oxidising n-dodecane radical cation (RH˙+) with f-element complexed 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) has been undertaken utilizing time-resolved electron pulse radiolysis/transient absorption spectroscopy and high-level quantum mechanical calculations. Lanthanide ion complexed species, [Ln((HEH[EHP])2)3], exhibited vastly increased reactivity (over 10× faster) in comparison to the non-complexed ligand in n-dodecane solvent, whose rate coefficient was k = (4.66 ± 0.22) × 109 M−1 s−1. Similar reactivity enhancement was also observed for the corresponding americium ion complex, k = (5.58 ± 0.30) × 1010 M−1 s−1. The vastly increased reactivity of these f-element complexes was not due to simple increased diffusion-control of these reactions; rather, enhanced hole transfer mechanisms for the complexes were calculated to become energetically more favourable. Interestingly, the observed reactivity trend with lanthanide ion size was not linear; instead, the rate coefficients showed an initial increase (Lu to Yb) followed by a decrease (Tm to Ho), followed by another increase (Dy to La). This behaviour was excellently predicted by the calculated reaction volumes of these complexes. Complementary cobalt-60 gamma irradiations for select lanthanide complexes demonstrated that the measured kinetic differences translated to increased ligand degradation at steady-state timescales, affording ∼38% increase in ligand loss of a 1 : 1 [La((HEH[EHP])2)3] : HEH[EHP] ratio system. [ABSTRACT FROM AUTHOR]

Herein, we apply three different copper-exchanged materials (Na–[Al]SBA-15, silica, Na–MCM-22) as hosts for a direct synthesis of CuI(1,1′-bis(diphenylphosphino)ferrocene = dppf) complexes in cationic ion exchange position. Using 31P MAS NMR spectroscopy, we show that identical complexes as after ion exchange are generated if the solids are applied as reactants directly. The homogeneity of copper exchanges is evaluated by EDX spectroscopy. Both CuI and CuII result in the formation of complexes, thereby oxidizing dppf. Cu-particles were not reactive. Optimized conditions for a maximized complex formation are identified applying quantitative 31P MAS NMR spectroscopy and ICP-OES. Only accessible copper in cationic position of the solids forms the complexes. This enables a quantification of the amount of copper in mesopores vs. the total copper amount. Thus, besides a new synthesis of the complex a suitable method for quantitative elucidation of the location of copper cations is demonstrated herein. [ABSTRACT FROM AUTHOR]

A configurationally-labile helical dye, 2,4,5,7-tetranitrofluorenone oximate, is used to probe complexes made of enantiopure macrocycles and mono/divalent metal ions. Induced electronic circular dichroism (ECD) and 1H NMR responses are amplified at room temperature only in the presence of K+ and Na+ ions despite larger binding efficiency with alkaline earth metal ions. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) are unique hybrid porous materials formed by combining metal ions or clusters with organic ligands. Thiol and thioether-based MOFs belong to a specific category of MOFs where one or many thiols or thioether groups are present in organic linkers. Depending on the linkers, thiol-thioether MOFs can be divided into three categories: (i) MOFs where both thiol or thioether groups are part of the carboxylic acid ligands, (ii) MOFs where only thiol or thioether groups are present in the organic linker, and (iii) MOFs where both thiol or thioether groups are part of azolate-containing linkers. MOFs containing thiol-thioether-based acid ligands are synthesized through two primary approaches; one is by utilizing thiol and thioether-based carboxylic acid ligands where the bonding pattern of ligands with metal ions plays a vital role in MOF formation (HSAB principle). MOFs synthesized by this approach can be structurally differentiated into two categories: structures without common structural motifs and structures with common structural motifs (related to UiO-66, UiO-67, UiO-68, MIL-53, NU-1100, etc.). The second approach to synthesize thiol and thioether-based MOFs is indirect methods, where thiol or thioether functionality is introduced in MOFs by techniques like post-synthetic modifications (PSM), post-synthetic exchange (PSE) and by forming composite materials. Generally, MOFs containing only thiol-thioether-based ligands are synthesized by interfacial assisted synthesis, forming two-dimensional sheet frameworks, and show significantly high conductivity. A limited study has been done on MOFs containing thiol-thioether-based azolate ligands where both nitrogen- and sulfur-containing functionality are present in the MOF frameworks. These materials exhibit intriguing properties stemming from the interplay between metal centres, organic ligands, and sulfur functionality. As a result, they offer great potential for multifaceted applications, ranging from catalysis, sensing, and conductivity, to adsorption. This perspective is organised through an introduction, schematic representations, and tabular data of the reported thiol and thioether MOFs and concluded with future directions. [ABSTRACT FROM AUTHOR]

We report three CoII-based complexes with the general formula [CoII(L)(X)2] by changing the halide/pseudo-halide ions [X = NCSe (1SeCN); Cl (2Cl) and Br (3Br)]. The obtained τ5 and CShM values confirm a distorted square pyramidal geometry around the CoII ion in all these complexes. In these three complexes, the central CoII ion is situated above the basal plane of the square pyramidal geometry. The extent of distortion from the ideal SPY-5 geometry differs upon changing the coordinating halide/pseudo-halide ion in these complexes. This essentially results in the alteration of the anisotropic parameter D and hence impacts the magnetic properties in these complexes. This phenomenon has been corroborated with the aid of theoretical investigations. All these complexes display field-induced SIM behaviour with magnetic relaxation occurring through a combination of processes depending on the applied dc magnetic field values and dilution. [ABSTRACT FROM AUTHOR]

We report a joint experimental and theoretical study of RuO2/TiO2 heterostructures. In the experimental section, mesoporous RuO2/TiO2 heterostructures were prepared by impregnation of mesoporous TiO2 nanoparticles which were synthesized from a new precursor, Na2[Ti(C2O4)3], in an aqueous solution of ruthenium(III) chloride followed by calcination at 300 °C. Using various techniques, the prepared TiO2 and RuO2/TiO2 heterostructures were extensively characterized. The photoelectocatalytic application of the as-prepared heterostructures was then investigated toward the hydrogen evolution reaction (HER). The results illustrated that RuO2 is dispersed uniformly on the TiO2 surface. The loading of RuO2 on TiO2 decreases the band gap energy and extends the absorption edge to the visible light region. This wide absorption extends the photoelectrocatalytic activity of RuO2/TiO2 heterostructures. To obtain a deeper understanding of the increase of the photoelectrocatalytic activity of RuO2/TiO2 heterostructures compared to pure TiO2, theoretical calculations at the density functional theory (DFT) level were performed on some model clusters of pure TiO2 and the RuO2/TiO2 heterostructure. The theoretical results elucidated that the recombination ratio of electron–hole pairs decreases effectively for RuO2/TiO2 compared to pure TiO2. [ABSTRACT FROM AUTHOR]

The subcomponent self-assembly of 4,6-dihydrazinopyrimidine and o-vanillin/salicylaldehyde with different DyIII salts leads to the formation of Dy2 (1–3) and grid-like Dy4 (4) compounds with formulas of [Dy2L(DMF)4(NO3)4]·2DMF (1), [Dy2L2(CH3COO)4(CH3OH)2]·10H2O (2), [Dy2L′2(CH3COO)4(CH3OH)2]·2H2O·2CH3OH (3) and [Dy4Na2L2(μ2-OH)2(PhCOO)8(CH3OH)(H2O)]·CH3CN·2CH3OH·7H2O (4). In all cases, the DyIII ions are nine coordinate but the different features of coordinated solvent molecules and anions result in diverse coordination geometries in their respective structures. Notably, by introducing various axial coordinating anions with different electronegativities (NO3−, CH3COO− and C6H5COO−), the effective energy barriers were progressively enhanced (52–207 K) in this system. Detailed magnetic studies for these complexes revealed obvious magnetic interactions in complex 1 and clear single molecule magnet (SMM) behavior with anisotropy barriers of 52, 56 and 58.4 K for 1–3, respectively. Moreover, we find that the incorporation of benzoates into the axial position of the DyIII ions in complex 4 leads to the occurrence of two clear distinct relaxation processes, with energy barriers of 94.9 and 207.2 K, respectively. This result presents an example of the effects of axial coordinating anions on the SMM behavior, providing a valid route towards enhancing the slow magnetic relaxation of 4f based SMMs via incorporating diverse coordination anions into the subcomponent self-assembly system. [ABSTRACT FROM AUTHOR]

Although progress has been made in the design and synthesis of chiral lanthanide clusters with pleasing structural connections and special shapes, assembly rules that guide their directional construction are still lacking. We reacted R/S -mandelic acid hydrazide, 2,3-dihydroxybenzaldehyde and DyCl3·6H2O under solvothermal conditions to obtain two octanuclear chirality clusters R-1 and S-1 , which are the enantiomers of each other. R/S -mandelic acid hydrazide and 2,3-dihydroxybenzaldehyde underwent an in situ reaction under "one-pot" conditions to generate a monohydrazone-type organic ligand R/S -mandelic acid hydrazide-2,3-dihydroxybenzaldehyde hydrazone (R/S -H2L). Four R/S -H2L ligands captured eight metal-centered Dy(III) ions and presented an annular arrangement, which assembled to form a pinwheel-shaped chiral cluster R/S-1. The benzene rings at the four vertices of R/S-1 can rotate freely as rotors. This is the first discovery of an annular growth mechanism during the self-assembly of lanthanide clusters. By changing the metal salt to Dy(NO3)3·6H2O, two twist-shaped hexanuclear clusters R-2 and S-2 , which are the enantiomers of each other were obtained. Four R/S -H2L and two R/S -H3L ligands captured six metal-centered Dy(III) ions, respectively, and were assembled through a linear growth mechanism to form the twist-shaped chiral clusters R/S-2. This is the first time that a linear growth mechanism has been proposed for the directional construction of lanthanide clusters with specific shapes. Circular dichroism results showed that R/S-1 and R/S-2 were both chiral clusters and enantiomers of each other. Magnetic studies showed that both R/S-1 and R/S-2 exhibit obvious single-molecule magnet (SMM) behaviors under zero-field conditions. This work is the first to propose an annular/linear growth mechanism for the design and synthesis of lanthanide clusters and allows the directional construction of chiral lanthanide clusters with special shapes and structural connections. [ABSTRACT FROM AUTHOR]

In this work, we report two supramolecular isomorphic dodecanuclear cobalt complexes, [Co12(mtz)3(L)6(NO3)2(OH)(N3)3]·(OH)3 (1) and [Co12(mtz)3(L)6(NO3)2(OH)(N3)(OAc)]·(OH)4 (2), (Hmtz = 5-methyl-1H-tetrazole, H2L = 7,7′-(ethane-1,1-diyl) diquinolin-8-ol) crystallizing in the P¯ space group with the same unit cell parameters. In 1 and 2, two pirate hat-like hexanuclear Co6(NO3)(L)3 units form the same dodecanuclear metal shell, but the ligands between the hexanuclear units as the core are distinct. The introduction of acetate anions leads to a blue shift of the absorption band in the visible region. Magnetism studies indicate an antiferromagnetic interaction between the CoII ions in the clusters. [ABSTRACT FROM AUTHOR]

To enhance light absorption in the visible region for the utilization of sunlight, eight mixed-valence polynuclear CuI/CuII clusters have been synthesized for evaluating their photothermal conversion performance. They are fabricated considering the ligand's electron density distribution inhomogeneity using 1,2,3-triazole (3N) or tetrazole (4N) and different mono-phosphine ligands. We report here the synthesis, crystal structure, characterization, optical properties, and photothermal conversion performance of these clusters. X-ray crystal structures reveal that those pentanuclear clusters are neutral clusters with octahedrally- coordinated copper(II) ion being surrounded by four tetrahedrally coordinated copper(I) ions. Interestingly, with the introduction of the mixed-valence centers, these compounds show additional light absorption centers in 350-600 nm via the IVCT transition mechanism, compared with our previously reported Cu(II) compounds. These clusters show excellent photothermal conversion performance, with an average equilibrium temperature (~60 °C) and a temperature increment (~40 °C), which are also superior to Cu(II) complexes (the average equilibrium temperature ~55 °C). This work proves that it is possible to design and prepare new polynuclear mixed-valence CuI/CuII clusters for achieving high-performance photothermal conversion materials. [ABSTRACT FROM AUTHOR]

This study presents a molecular surface modification approach to synthesizing a family of silver chalcogenolate clusters (SCCs) containing the same [Ag12S6] core and different surface-bonded organic ligands (DMAc or pyridines; DMAc = dimethylacetamide), with the aim of tuning the luminescence properties and increasing the structural stability of the SCCs. The SCCs displayed strong and tuneable luminescence emissions at 77 K (from green to orange to red) as influenced by the peripheral pyridine ligands. In addition, SCC 5 protected by pyridine molecules was stable in ambient air, humid air and even liquid water for a long time (up to 1 week), and it was more structurally stable than SCC 1 bonded with DMAc molecules under the same conditions. The high structural stability of SCC 5 can be explained by the ability of pyridine molecules to form strong coordination bonds with silver atoms. This study offers a new way of designing structurally stable metal nanoclusters with tuneable physicochemical properties. [ABSTRACT FROM AUTHOR]

The synthesis, solution studies, photochemical properties and the X-ray structure of a chromone based fluorescent PdII complex are reported. The ligand contains two chromone units linked as side arms to an ethylenediamine moiety; in the PdII complex the metal ion preorganizes the two hydroxychromone units forming a rigid structure with a negatively charged pocket formed by four oxygen atoms that is able to interact with hard metal cations, such as ions, giving rise to stable bimetallic complexes. Upon interaction with LaIII and GdIII, in particular, the emission intensity at 423 nm increases by a factor of 2 and 8, respectively, while the other rare earth ions quench the fluorescence. Spectrofluorimetric studies on real matrices showed the possibility to use this system as a selective fluorescence probe to detect and trace the presence of Gadolinium in environmental water acting as an OFF–ON chemosensor, with a LOD of 0.4 ppm and a LOQ of 1.2 ppm. [ABSTRACT FROM AUTHOR]

A photoelectrochemical (PEC)–electrochemical (EC) dual-mode biosensing strategy based on COF@MOF heterostructure was developed for efficiently analyzing Cr(III) ions. A two-dimensional phthalocyanine-based COF (CoPc-PT-COF) was in situ grown on a Cu-based MOF (Cu-MOF) substrate via covalent binding between carboxyl groups in Cu-MOF and amino groups in CoPc-PT-COF (denoted as CoPc-PT-COF@Cu-MOF). The coexistence of both phthalocyanine and bipyridine in CoPc-PT-COF@Cu-MOF affords the outperformed electro- and photo-activities, thus serving as a photoelectric beacon with favorable energy-band configuration and amplified electrochemical response. Due to the high porosity and rich functionality of the obtained heterostructure, the DNA strands can be tightly anchored over CoPc-PT-COF@Cu-MOF via diverse interactions. Thanks to the specific recognition between DNA strands and Cr3+ ions, the CoPc-PT-COF@Cu-MOF-based biosensor can be used to determine Cr3+ ions in an aqueous environment by PEC–EC mode. The gained biosensor shows an extremely low limit of detection (LOD) of 14.5 fM (for PEC) and 22.9 fM (for EC) within the Cr3+ concentration range from 0.1 pM to 100 nM, along with high selectivity, good reproducibility and stability. Moreover, this novel biosensor exhibits acceptable applicability for analyzing the trace Cr3+ from diverse samples (e.g., river and tap water). As a result, this work provides new insights into the construction of a high-efficiency PEC–EC dual-mode biosensor for detecting heavy metal ions from complex environments. [ABSTRACT FROM AUTHOR]

Transition metals have a long history in heterogeneous catalysis. Noble or precious transition metals have been widely used in this field. The advantage of noble and precious metals is obvious in 'heterogeneous catalysis'. However, the choice of Earth abundant metals is a sustainable alternative due to their abundance and low cost. Preparing these metals in the nanoscale dimension increases their surface area which also increases the catalytic reactions of these materials. Nevertheless, metals are unstable in the nanoparticle form and tend to form aggregates which restrict their applications. Loading metal nanoparticles (MNPs) into highly porous materials is among the many alternatives for combating the unstable nature of the active species. Among porous materials, highly crystalline metal–organic frameworks (MOFs), which are an assembly of metal ions/clusters with organic ligands, are the best candidate. MOFs, on their own, possess catalytic activity derived from the linkers and metal ions or clusters. The catalytic properties of both non-noble metal nanoparticles (MNPs) and MOFs can be improved by loading non-noble MNPs in MOFs yielding MNP@MOF composites with a variety of potential applications, given the synergy and based on the nature of the MNP and MOF. Here, we discussed the synthesis of MNP@MOF materials and the applications of non-noble MNP@MOF materials in heterogeneous catalysis. [ABSTRACT FROM AUTHOR]

Iridium complexes have been widely applied as molecular sensors because of their rich photophysical properties, including large Stokes shifts, long emission lifetimes, environment-sensitive emissions, and high luminescence quantum yields. In this paper, we review the recent development and application of iridium complexes as probes for ions, anions, gaseous species, organic molecules, small biomolecules, biomacromolecules, and subcellular organelles. Our outlook for iridium-based probes is also discussed. [ABSTRACT FROM AUTHOR]

Indium metal–organic frameworks (In-MOFs) based on pyridylcarboxylate ligands represent a subclass of MOFs featuring diverse structures, a high stability, and various properties. This review discusses the different aspects of In-MOFs including their design, synthesis and structures as well as their typical potential applications in adsorption and separation, catalysis, and chemical sensors. Importantly, the effect of pyridine on the properties and stability of frameworks has been carefully studied. The introduction of a pyridine group not only significantly enriches clusters of In3+ ions, but also enables flexible, controllably synthesized ionic or neutral frameworks to be fabricated. Based on this, we suggest that this type of In-metal organic framework (MOF) should receive more attention in the field of MOF design. [ABSTRACT FROM AUTHOR]

A bimetallic Cu(II) complex as a novel antitumor chemodynamic therapy agent with glutathione (GSH) depletion properties is successfully synthesized and well characterized. In tumor cells, the Cu2+ ions of the complex are reduced to Cu+ ions by GSH and then catalyzed by the overexpressed H2O2 to generate highly cytotoxic hydroxyl radicals (˙OH) that kill cancer cells. The complex is quickly taken up by cancer cells and distributed in multiple organelles including mitochondria and the nucleus. The complex demonstrates good cytotoxicity toward various cancer cell lines. However, its toxicity toward normal cells is significantly lower than that toward cancer cells due to the limited expression of H2O2. In addition, the complex could arrest the cell cycle of the G0/G1 phase, thereby inducing apoptosis rather than necrosis. [ABSTRACT FROM AUTHOR]

Three di-nuclear DyIII complexes [Dy2(H2L)2(tfa)]·Cl·3DMF (1), [Dy2(H2L)2(MeO)(SCN)]·MeOH (2) and [Dy2(H2L)2(MeOH)Cl]·Cl·2MeOH (3) were synthesized and structurally and magnetically characterized. The Dy1/Dy2 centers in these complexes are all nine-coordinate with spherical capped square antiprism (local C4v symmetry) environments. All complexes display single-molecule magnet (SMM) behavior under zero applied dc field with their properties dependent on the nature of the magnetic interactions between the DyIII ions. Ab initio calculations substantiate that all DyIII ions show a weakly axial crystal-field environment with the exception of one of the DyIII ions in complex 2. The ground Kramers doublets show modest amounts of quantum tunneling of magnetization that gets blocked by the interaction between the DyIII ions, leading to a thermally activated slow relaxation of magnetization. The interaction between the ions is ferromagnetic and mostly originates from the dipolar interaction. However, anti-ferromagnetic intermolecular interaction plays an important role and in the case of complex 2 it is sufficiently strong to mask the ferromagnetic intramolecular interaction. [ABSTRACT FROM AUTHOR]

A newly designed and synthesized half-condensed organic moiety 2-hydroxy-5-methyl-3-[(2-phenylamino-phenylimino)-methyl]-benzaldehyde (HL′) and a Zn2L4 complex sequentially detect Zn2+ and H2PO4− ions as low as 1.13 nM and1.23 μM, respectively. HL′ and a dinuclear Zn(II) complex of in situ generated L− in a solution formulated as Zn2L4 under investigation were characterized by physicochemical and spectroscopic studies along with detailed structural analyses by single-crystal X-ray crystallography. The selectivity and sensitivity of HL′ towards Zn2+ ions and of the Zn2L4 complex towards H2PO4− ions are based on CHEF and via displacement pathways, respectively. Dual sensing of Zn2+ ions and H2PO4−ions in an aqueous medium via "Green-Blue-Green" emission with the reversible transformation of in situ formed HL′ to HL was established by detailed electronic absorption and emission spectroscopic studies. This non-cytotoxic probe (HL′, i.e. produced HL in solution) and Zn2L4 complexes are able to monitor the subcellular distribution changes of Zn2+ and H2PO4− ions, respectively, by fluorescence microscopy using the human semen sample. [ABSTRACT FROM AUTHOR]

The present work for the first time reports an application of the thiacalix[4]arene scaffold for the preparation of Tb3+ complexes possessing high thermal luminescence sensitivity in the physiological temperature range of 20–50 °C. Non-substituted thiacalix[4]arenes form luminescent complexes with Tb3+ ions, but they do not reveal any meaningful thermal sensitivity. To solve this problem, an upper-rim bromination of thiacalix[4]arenes, as well as distal bromination along with the embedding of two 1,3-diketone substituents are proposed as new simple synthetic approaches to enhance the thermal luminescence sensitivity of the Tb3+ complexes. A combination of mass spectrometry, NMR, UV-Vis and luminescence spectroscopy with quantum chemical calculations reveals a dimeric structure of the complexes formed by thiacalix[4]arenes with Tb3+ ions in DMF solutions. The steady-state luminescence of the Tb3+ complexes has demonstrated more than one order higher thermal sensitivity for the complexes of bromo-substituted ligands in comparison with the non-substituted thiacalix[4]arenes. The reasons for such behavior are discussed. The results highlight new opportunities for the thiacalix[4]arene platform for controlling ligand-to-metal energy transfer in terbium complexes and tuning their thermo-responsive luminescence properties. [ABSTRACT FROM AUTHOR]

Synthesis of a pincer-type linear nitrosyl complex [Rh(PtBu2CNEt2)(NO)]+ (3+) is described. The product and all intermediates involved were fully characterized by FTIR, NMR, cyclic voltammetry and X-ray crystallography. Attempts at obtaining (3+) from its chlorinated precursor Rh(PCN)(NO)Cl (2) revealed that a relative stabilization of this complex ion is introduced by the BArF− counteranion, as other counteranions—PF6−, BF4− and triflate—proved to coordinate to the metal center. Redox reactivity both of (3+) and of that of its five-coordinate derivatives (2) and [Rh(PCN)(NO)(CH3CN)]+ (4+) was found to distinguish itself from analogous PCP complexes due to a relative stabilization of higher oxidation states. Oxidation of these three complexes was studied by FTIR spectroelectrochemistry. Reduction of complex (3+) to yield a short-lived {RhNO}9 species [Rh(PCN)(NO)]˙ (3˙) was also carried out. Complex (3˙) was proved able to activate carbon–halogen bonds in aryl halides, in much a similar way as that of its PCP analogue. Complex (3+) was also seen to establish a linear ↔ bent nitrosyl equilibrium upon addition of CO which could not be fully displaced with excess CO. [ABSTRACT FROM AUTHOR]

The discovery of low-valent Zn compounds resulted in the renaissance of organometallic Zn complexes. Polyhedral clusters of tetrel elements can interact with Zn atoms either as Lewis donors or by incorporation of the Zn atoms as additional cluster vertices. Herein we report the reactions of ZnR2 (R = ethyl (Et), pentamethylcyclopentadiene (Cp*), phenyl (Ph) and 1,3,5-trimethylbenzene (Mes)) with Zintl ions of the types [E4]4− (E = Ge, Sn) and [Ge9]4− in liquid ammonia. Besides the desired Zintl ion complexes, intermediates were isolated that give insight into the reaction of organo Zn compounds in liquid ammonia. Three ions, [(η3:η3-Ge4)(ZnEt)2]2− (1a), [(η2-Sn4)Zn(η2-Sn4)]6− (2a) and [(η4-Ge9)(ZnEt)]3− (3a), were obtained and characterized by means of single crystal X-ray diffraction analysis. Furthermore, amides [(ZnPh2)2(μ2-NH2)2]2− (4a) and {[Zn(μ2-NH2)4][(ZnEt)2(μ2-NH2)2]2}2− (5a) were formed during the reactions, together with the addition products [ZnPh3]− (6a) and [ZnMes3]− (7a) and an anion [Cp*]− (8a), suggesting the following reaction sequence: in liquid ammonia the Zintl anions form amides, which then serve as ligands for ZnR2 molecules. The NH2− ligands weaken the corresponding Zn–R bonds, and thus bond cleavage and the addition of the Zintl anion to the Zn ion can take place, additionally promoted by the trapping of the leaving group R− by unreacted Zn organyls with the formation of [ZnR3]−. [ABSTRACT FROM AUTHOR]

Chemotherapeutic metal-based compounds are effective anticancer agents; however, their cytotoxic profile and significant side effects limit their wide application. Natural products, especially flavonoids, are a prominent alternative source of anticancer agents that can be used as ligands for the generation of new bioactive complexes with metal ions of known biochemical and pharmacological activities. Herein, we present the synthesis and detailed structural and physicochemical characterizations of three novel complex assemblies of Ga(III) with the flavonoid chrysin and the ancillary aromatic chelators 1,10-phenanthroline, 2,2′-bipyridine and imidazole. The complexes constitute the only crystallographically characterized structures having a metal core from the boron group elements and a flavonoid as the ligand. The in vitro biological evaluation of the three complexes in a series of cancer cell lines of different origin established their cytotoxicity and ROS generating potential. In particular, the Ga(III)–chrysin–imidazole complex displayed the highest anticancer efficacy against all cancer cell lines with IC50 values in the low micromolar range (<1.18 μM), a result worth further investigation. [ABSTRACT FROM AUTHOR]

Diphenic acid (H2dip) has been used to synthesize nine homo- or heterometallic uranyl ion complexes under solvo-hydrothermal conditions. The diphenate ligand dip2− adopts different coordination modes, mixtures of κ2-O,O′-chelation by individual carboxylate groups, chelation involving both carboxylate groups, and bridging, resulting in different associations of the cations present. [UO2(dip)] (1), [UO2(dip)(bipy)] (2), and [UO2(dip)(phen)] (3) crystallize as monoperiodic coordination polymers, complex 1 with the bridging and both chelation modes of the ligand, and 2 and 3 with only the bis-κ2-O,O′-chelated mode and further chelation by 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen). The two isomorphous complexes [H2NMe2]2[(UO2)2(dip)3] (4) and [(UO2)2Ag2(dip)3(H2O)(CH3CN)] (5) display ladder-like monoperiodic arrangements with the hydrogen bonded H2NMe2+ or carboxylate-bound, decorating Ag+ cations occupying similar positions within the chains. [Ni(R,S-Me6cyclam)(H2O)2][UO2(dip)2] (6) contains a discrete dianionic mononuclear species, while [(UO2)2(dip)2(Hdip)2Ni(cyclam)]·2H2O·2CH3CN (7) crystallizes as a monoperiodic, heterometallic polymer, with further formation of layers through reciprocal hydrogen bonding of the carboxylic acid groups. A discrete dinuclear dianionic complex is present in [Cu(R,S-Me6cyclam)][UO2(dip)(NO3)]2 (8), which crystallizes together with [(UO2)3(dip)4Cu(R,S-Me6cyclam)(H2O)2]·6H2O (9), a diperiodic assembly in which uranyl-containing dimeric units are assembled in chains through diaxial carboxylate coordination of Cu(R,S-Me6cyclam)2+ cations, with further bridging by uranyl cations generating a network with the fes topology. The uranyl emission spectra of complexes 3, 4 and 5 show the usual vibronic fine structure, while uranyl emission in 7 is largely quenched. [ABSTRACT FROM AUTHOR]

The most effective way to understand reaction mechanisms and kinetics is to identify the reaction intermediates and determine the possible reaction patterns. The influencing factors that must be considered in the self-assembly of clusters are the type of ligand, metal ion, coordination anion and the pH of the solution. However, changes in ligand substituents resulting in different self-assembly processes to obtain different types of structures are still very rare, especially with –H and –CH3 substituents, which do not exert significant steric hindrance effects. In this study, planar mononuclear Ni(L1)2 (L1 = 2-ethoxy-6-(iminomethyl)phenol) was dissolved in methanol and combined with Dy(NO3)3·6H2O for 48 h at room temperature to obtain a butterfly-like Ni2Dy2 cluster ([Dy2Ni2(L1)4(CH3O)2(NO3)4], 1). The Dy(III) ions in cluster 1 are in an O8N coordination environment, and the Ni(II) ions are in an O5N coordination environment. High-resolution electrospray ionization mass spectrometry (HRESI-MS) was used to track species changes during the formation of cluster 1. Six key intermediate fragments were screened, and the self-assembly mechanism was proposed as Ni(L1)2 → HL1 + NiL1 → DyL1/Ni(L1)2′ → DyNi(L1)2 → Dy2Ni2(L1)4. Through this assembly mechanism, we found that Ni(L1)2 was first cleaved into HL1 + NiL1 and then further assembled to obtain 1. Another butterfly-like tetranuclear heterometallic cluster ([Dy2Ni2(L2)4(CH3O)2(NO3)4], 2) was obtained using planar mononuclear Ni(L2)2 (L2 = (E)-2-ethoxy-6-((methylimino)methyl)phenol) with –CH3 substitution on the nitrogen atom under the same reaction conditions. The structural analysis of cluster 2 showed that the Dy(III) ions are in an O9 coordination environment, and the Ni(II) ions are in an O4N2 coordination environment. HRESI-MS was used to trace species changes during the formation of 2, and the assembly mechanism was proposed as Ni(L2)2 → DyNi(L2)2 → Dy2Ni(L2)2 → Dy2Ni2(L2)4. Analysis of the assembly mechanism of 2 showed that Ni(L2)2 was twisted during the reaction, and its coordination point was exposed to capture the Dy(III) ions. Finally, Dy(NO3)3·6H2O was replaced with NaN3 to obtain a [Ni2Na2(L2)4(N3)4] cluster (3) under the same reaction conditions and verify the above-mentioned torsion step. HRESI-MS was also used to trace the assembly process, and the assembly mechanism was proposed as Ni(L2)2 → NiNa(L2)2 → NiNa2(L2)2 → Ni2Na2(L2)4. Herein, the effect of interference from substitution and the regulation self-assembly process were discovered in the formation of 3d–4f heterometallic clusters, and different types of coordination clusters were obtained. [ABSTRACT FROM AUTHOR]

A novel flexible "N", "O"-rich hydrazide-based Schiff base chemoreceptor, 2-(benzamido)-N′-((pyridin-2-yl)methylene)benzohydrazide (L), was designed, synthesised and characterised via1H-NMR, IR spectroscopy, ESI-MS spectrometry and single-crystal XRD analysis. The receptor showed a colorimetric and fluorometric "turn on" response in the presence of only Ni2+ ions in methanol–Tris-HCl buffer medium (10 mM, pH 7.2, 1 : 1 v/v). The Job plot analysis revealed that the receptor forms a 2 : 1 complex with Ni2+ ions, which was further confirmed via the ESI-MS analysis. A single crystal of the L–Ni2+ complex (2) was also isolated. The detection limit was calculated to be 1.8 μM colorimetrically and 1.18 μM fluorometrically, which are much lower than those recommended as per the WHO guidelines for drinking water. The experimental results were further supported by DFT studies. The chemosensor L was applied for the recovery of contaminated water samples, building of molecular logic gate, smart phone-based analysis and live cell imaging. [ABSTRACT FROM AUTHOR]

Three new complexes forming a dynamic system and given by the following formulae: [Cu2(bpy)4Fe(ox)3]NO3·H2O 1, [Fe(bpy)3]2[Fe(ox)3]NO3·10H2O 2 and [Cu(bpy)3]2[Fe(ox)3]NO3·10H2O 3 (bpy – 2,2′-bipyridine, ox – oxalate), were synthesized from a methanol–water mixture or water, and characterized structurally, spectroscopically and magnetically. Compound 1 contains trinuclear [(bpy)2Cu(μ-ox)Fe(ox)(μ-ox)Cu(bpy)2]+ cations, while 2 and 3 can be classified as isomorphous ionic compounds, with alternately arranged hydrophobic and hydrophilic layers of mononuclear complex ions. The green crystals of 1 are perfectly stable in air, whereas in selected solvents they undergo irreversible solvent-assisted recrystallization towards red crystals of 2, which is also accompanied by the appearance of mononuclear blue copper complexes with oxalate, 2,2′-bipyridine and aqua ligands, already described in the literature. The above crystallization/recrystallization processes indicate variable solution contents. The whole effect is accelerated by both the increased temperature and day light irradiation, however, different products from the pool prevail under various conditions. The observed transformation can be understood in terms of thermodynamic and kinetic control, involving the known photo-activity of [Fe(ox)3]3− moieties and the effect of quadruple aryl embrace (QAE) on the stability of the crystal network. Considering the presence of FeIII–ox–CuII connectivity in 1 we performed detailed magnetic studies and theoretical calculations for this compound. Due to the strong asymmetry of Cu–O bonds the antiferromagnetic coupling is rather weak, with JCu–Fe being ca. −3.4 cm−1 (using Hamiltonian of the type H = −JCu–Fe(SCu1SFe + SFeSCu2) −JCu–Cu(SCu1SCu2)). We found that these values are very close to those predicted by B3LYP/6-311G* calculations. [ABSTRACT FROM AUTHOR]

Five novel coordination polymers (CPs), formulated as {[Co3(μ4-cpboda)2(μ1,1-OH2)2(2,2-bipy)2]·1.5DMF·2H2O}n (1), {[Co3(μ3-cpboda)2(4,4′-bpy)3(H2O)2]·4H2O}n (2), {[Co(μ2-H2cpboda)2(1,4-bib)3(H2O)2]·H2O·DMF·1.5HCOOH}n (3), [Cd(μ3-Hcpboda)(1,4-bib)]n (4), and {[Cd3(μ4-cpboda)2(μ1,1-OH2)2(phen)2]·2DMF·1.5H2O}n (5) (H3cpboda = 3,3′-((5-carboxy-1,3-phenylene)bis(oxy))dibenzoic acid, 2,2-bipy = 2,2-bipyridine, 4,4′-bpy = 4,4′-bipyridine, 1,4-bib = 1,4-di(1H-imidazol-1-yl)benzene, phen = 1,10-phenanthroline) have been synthesized under solvothermal conditions and characterized by elemental analyses (EAs), single-crystal X-ray diffraction analyses, X-ray powder diffraction analyses (PXRD), FT-IR spectra, and thermogravimetric analyses (TGAs). The structural analyses reveal that these complexes have four 2D coordinate polymers and one 3D framework, in which metal ions are in octahedral coordination geometries in 1–3 and 5, but seven-coordinated disordered pentagonal bipyramids in 4. Complexes 1 and 5 represent linear trinuclear [M3(μ1,1-OH2)2(μ1,3-COO)4] SBUs in 1 (M = Co(ii)) and in 5 (M = Cd(ii)) based on a 3,4,6-connected net with a point symbol (32·4)2(32·83·9)2(34·42·82·94·103) net, complex 2 exhibiting a (3-c)2(4-c)(4-c)2 3D structure with the (52·6·82·9)2(52·62·92)(52·6)2 topology and complexes 3 and 4 having a novel 2D framework with the point symbol of (44·62). Magnetization analyses disclose the antiferromagnetic (AF) behaviors between Co(ii) ions in complexes 1 & 3 and S = 3/2 (Co2+) spin Heisenberg chains with alternating magnetic sequences (F/F/AF)n in 2. Fluorescence measurements indicate that 4 and 5 are promising luminescence sensors for the detection of CrO42− and Cr2O72− anions in aqueous solution. [ABSTRACT FROM AUTHOR]

Nine uranyl ion complexes have been synthesized using two kinds of sulfonate-containing ligands, i.e. 2-, 3- and 4-sulfobenzoic acids (2-, 3- and 4-SBH2), which include additional carboxylic donors, and p-sulfonatocalix[4]arene (H8C4S), with additional phenolic groups, and [Ni(cyclam)]2+, [Cu(R,S-Me6cyclam)]2+ or PPh4+ as counterions. [Ni(cyclam)][UO2(4-SB)2(H2O)2]·2CH3CN (1) and [Ni(cyclam)][UO2(3-SB)2(H2O)2] (2) are molecular species in which only the carboxylate groups are coordinated to uranyl, the sulfonate groups being essentially hydrogen bond acceptors. In contrast, uranyl κ1-O(S);κ1-O(C)-chelation is found in the four complexes involving 2-SB2−, different bridging interactions producing diverse geometries. [UO2(2-SB)2Ni(cyclam)]·H2O (3) crystallizes as a two-dimensional (2D) assembly with fes topology, in which uranyl ion dimeric subunits are bridged by six-coordinate NiII cations. Complexes [UO2(2-SB)2Cu(R,S-Me6cyclam)]2·2H2O (4) and [(UO2)2(2-SB)2(C2O4)Cu(R,S-Me6cyclam)] (5), obtained together from the same solution, are a molecular tetranuclear complex and a 2D species with fes topology, respectively, depending on the coordination number, 5 or 6, of the CuII cation. The complex [PPh4]2[(UO2)2(2-SB)3(H2O)]·H2O (6) is a one-dimensional (1D), ribbon-like coordination polymer with a layered packing of alternate cationic and anionic sheets. No heterometallic complex was obtained with H8C4S, but the copper-only compound [{Cu(R,S-Me6cyclam)}5(H3C4S)2]·17H2O (7) displays mixed coordination/hydrogen bonding association of the copper azamacrocycle complex with the phenolic groups. The complexes [PPh4]5[UO2(H4C4S)(H2O)4][UO2(H3C4S)(H2O)4]·14H2O (8) and [PPh4]3[UO2(H3C4S)(H2O)3]·9H2O (9) were crystallized from the same solution and are a molecular complex and a 1D polymer, respectively, with monodentate sulfonate coordination to uranyl, while [PPh4]2[UO2(H4C4S)(H2O)3]·11H2O (10) is also a 1D polymer. The anionic complexes in the last three complexes form layers (9) or double layers (8 and 10) separated from one another by hydrophobic layers of PPh4+ cations. The balance between coordination and hydrogen bonding interactions with the macrocyclic ligands provides an indication of the energy of the sulfonate coordinate bond. Complex 6 is the only luminescent species in this series, albeit with a low quantum yield of 3%, and its emission spectrum is typical of a uranyl complex with five equatorial donors. [ABSTRACT FROM AUTHOR]

The solution- and solid-state interactions between the octadentate siderophore mimic 3,4,3-LI(1,2-HOPO) (343HOPO) and group IV metal ions were investigated using high-resolution mass spectrometry, liquid chromatography, UV-visible spectrophotometry, metal-competition batch titrations, and single crystal X-ray diffraction. 343HOPO forms a neutral 1 : 1 complex, [HfIV343HOPO], that exhibits extreme stability in aqueous solution, with a log β110 value reaching 42.3. These results affirm the remarkable charge-based selectivity of 343HOPO for octacoordinated tetravalent cations with a Hf(iv) complex 1021 more stable than its Lu(iii) analogue. Moreover, [HfIV343HOPO] and its Zr(iv) counterpart show exceptional robustness, with the ligand remaining bound to the cation over a very broad pH range: from pH ∼ 11 to acidic conditions as strong as 10 M HCl. In stark contrast, Ti(iv)-343HOPO species are far less stable and undergo hydrolysis at pH as low as ∼6, likely due to the mismatch between the preferred hexacoordinated Ti(iv) ion and octadentate 343HOPO ligand. The extreme charge-based and denticity-driven selectivity of 343HOPO, now observed across the periodic table, paves the way for new selective sequestration systems for radionuclides including medical 44Ti, 89Zr or 177Lu/Hf isotopes, toxic polonium (Po) contaminants, as well as rutherfordium (Rf) research isotopes. Furthermore, despite the lack of a chiral center in 343HOPO, its complexes with metal ions are chiral and appear to form a single set of enantiomers. [ABSTRACT FROM AUTHOR]

Pt(ii) and Rh(iii) readily form complexes with 3-methyl-5-aryl-1,2-tellurazole 2-oxides (L = (3-Me-5-Ar-1,2-C3HTe(NO)). The aryl group is either phenyl or 3,5-di-tert-butylphenyl, the latter case being a new derivative with enhanced solubility. The compound [Pt(3-Me-5-(3,5-tBu2C6H3)-1,2-C3HTe(NO))4](BF4)2 crystallizes in the P21/C space group featuring a square planar complex in the lattice. The crystal of [RhCl2(3-Me-5-(C6H5)-1,2-C3HTe(NO))4](BF4) belongs to the I4̅ space group and contains an octahedral complex. In both instances, the iso-tellurazole N-oxide molecules are linked by Te…O chalcogen bonding interactions confirming an annular tetramer that binds the metal ion as a κ4Te macrocycle in a boat conformation. Low-frequency shifts of the 125Te magnetic resonance upon coordination and the observation of 125Te–195Pt and 125Te–103Rh 1J coupling constants indicate that the complexes are stable species in solution. The complex ions were also observed in the electrospray mass spectra. [ABSTRACT FROM AUTHOR]

The initial employment of α-benzoin oxime (bzoxH2) in metal cluster chemistry has provided access to a new family of decanuclear CuIIcomplexes with a loop or single-strand wheel topology; the CuII10clusters are antiferromagnetically-coupled with an S= 0 spin ground state, as expected for even-membered loop arrays of CuIIatoms. [ABSTRACT FROM AUTHOR]

A dodecanuclear FeIII complex, consisting of two {Fe6} units coupled across a single hydroxy-bridge and a cage-like PdII trimer were synthesised using the highly branched, pentadecadentate chelating ligand cis,cis-1,3,5-cyclohexanetriamine-N,N,N',N',N'',N''-hexaacetic acid (H6hact). [ABSTRACT FROM AUTHOR]

Electrospray ionization (ESI) of solutions containing deoxyguanosine (dG) and tridentate platinum chloride complexes yields clusters of general formula [PtII(L)(dG)n]2+, where L = 2,2':6',2'' terpyridine (terpy), or diethyltriamine (dien). When these clusters were mass selected and subjected to collision induced dissociation (CID), the primary fragmentation channels arise from loss of dG and protonated dG to yield the fragment ions [PtII(L)(dG)n-x]2+ and [PtII(L)(dG)n-x-H]+ respectively. The relative abundances of the [PtII(L)(dG)n-x]2+ fragments depend on the nature of the ligand, L. The most abundant peaks observed were: n-x = 5 for terpy and n-x = 4 for dien. In order to further understand these gas phase reactions, molecular dynamics calculations were carried out. These simulated collision calculations not only predict with fidelity the experimental profiles for the relative abundances for the [PtII(L)(dG)n-x]2+ fragments, for both terpy and dien ligand systems, but they also provide structural insights into the complex interplay of hydrogen bonding and stacking interactions within these clusters. [ABSTRACT FROM AUTHOR]

Electrospray ionization (ESI) of solutions containing deoxyguanosine (dG) and tridentate platinum chloride complexes yields clusters of general formula [PtII(L)(dG)n]2+, where L = 2,2′:6′,2″ terpyridine (terpy), or diethyltriamine (dien). When these clusters were mass selected and subjected to collision induced dissociation (CID), the primary fragmentation channels arise from loss of dG and protonated dG to yield the fragment ions [PtII(L)(dG)n−x]2+and [PtII(L)(dG)n−x-H]+respectively. The relative abundances of the [PtII(L)(dG)n−x]2+fragments depend on the nature of the ligand, L. The most abundant peaks observed were: n−x = 5 for terpy and n−x = 4 for dien. In order to further understand these gas phase reactions, molecular dynamics calculations were carried out. These simulated collision calculations not only predict with fidelity the experimental profiles for the relative abundances for the [PtII(L)(dG)n−x]2+fragments, for both terpy and dien ligand systems, but they also provide structural insights into the complex interplay of hydrogen bonding and stacking interactions within these clusters. [ABSTRACT FROM AUTHOR]