Complex Ions Research Articles

Supramolecular Co (II) Complex Fabricated From Adenine Derivative: Synthesis, Crystal Structure, Hirshfeld Surface, DFT Optimization, Anticancer, and Molecular Docking Studies

ABSTRACTThis article presents the synthesis of a novel mononuclear Co (II) complex [Co(9‐BuA)2Cl2] (1), its characterization, supramolecular packing pattern, theoretical calculations, anticancer properties, and molecular docking studies. Complex 1 was generated from 9‐butyl adenine (9‐BuA) building block and characterized by spectroscopic methods (FT‐IR, mass, elemental analysis) and single crystal X‐ray diffraction analysis. The cobalt (II) ion in complex 1 is distorted in its tetrahedral environment. The Co+2 is coordinated to the two rare N1 binding sites of the pyrimidinate moiety of two 9‐BuA ligands and two chlorine atoms occupying the axial positions. Both intramolecular and intermolecular hydrogen bonds support the formation of supramolecular assembly and stabilize the crystal structure. The nature of the intermolecular interactions in the supramolecular network was also decoded by Hirshfeld surface analysis and molecular surface contours (dnorm). The percentage contributions are represented by 2D fingerprint plots. The average energy between dimers was determined by the energy framework analysis, and the crystal packing's three‐dimensional topology was also investigated. Density functional theory (DFT) has been used to ascertain the geometry and interactions in the complex. The cytotoxic effects of Co (II) complex 1 and corresponding 9‐BuA ligand were investigated in Dalton's lymphoma (DL) malignant cancer cells and on normal peripheral blood mononuclear cells (PBMCs) to evaluate their anticancer activity. Finally, molecular docking analyses have been carried out to analyze the nature of molecular interactions between Co (II) complex 1 and the receptor.

Complexes of Alkaline Earth Metal Ions with the Cyclodimethylsiloxane ligands D7, D8 and D9 (D = Me2SiO)

We present complexes of alkaline earth metal ions with the large cyclodimethylsiloxane D7, D8 and D9. The compounds prepared are [Mg(D7)(H2O)2][GaI4]2 (1), [Ca(D8)][GaI4]2 (2), [Sr(D8)][GaI4]2 (3), [Ba(D8)][GaI4]2 (4), [Ca(D9)][GaI4]2 (5), [Sr(D9)][GaI4]2 (6) and [Ba(D9)][GaI4]2 (7). Single‐crystal X‐ray diffraction and multinuclear NMR spectroscopy were used to analyze the prepared compounds and coordination modes in the solid state and in solution.

A novel corrosion inhibitor for copper in sulfuric acid media: Complexation of iodide ions with Benincasa Hispida leaf extract

In the context of green and low-carbon development, the rapid development of industry brings the problem of metal corrosion costs increase, metal corrosion protection methods are of great concern. Extracts from Benincasa hispida leaves (BHLE), which were obtained through pressurised liquid extraction, were employed as a inhibitor for copper corrosion in 0.5 M H2SO4. Their composition and anti-corrosion properties were subsequently analyzed and evaluated. The electrochemical analysis results indicated that BHLE functions as a cathodic-type corrosion inhibitor. The anti-corrosion performance intensifies with the increase in concentration but diminishes gradually as the temperature rises, when the concentration of BHLE is 400 mg/L, the corrosion inhibition efficiency can reach 91.82 %, when the concentration of added potassium iodide reaches 16 mg/L the slow-release efficiency of the compounded corrosion inhibitor reaches 96.92 %. The addition of I− strengthens the inhibition efficiency through the adsorption form dominated by competitive adsorption. The adsorption of BHLE onto the surface of copper follows the Langmuir monolayer adsorption model.

Dynamics of ionic liquid-polymer gel membranes-Insight from NMR relaxometry for [BMIM][BF4]-PVDF-HFP systems.

1H spin-lattice relaxation experiments have been performed for ionic liquid-polymer gel membranes, including 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]) and poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) with different proportions. The experiments have been performed in a broad range of resonance frequencies (from about 5Hz to 40MHz) vs temperature and complemented with analogous studies for [BMIM][BF4] in bulk as a reference. A model of the relaxation processes in the membranes has been proposed. The model includes two relaxation contributions. One of them corresponds to the concept of restricted, two-dimensional translation diffusion with a residence lifetime, while the second one has the form characteristic of polymers (mathematically similar to the limiting behavior of two-dimensional translation diffusion with a very long residence lifetime). The extensive dataset has been consistently interpreted in terms of the model, revealing two dynamical processes on the time scales of 10-7s (for the second relaxation contribution) and 10-9s (for the first one). The relationship of these relaxation contributions to the motion of the polymer or ionic liquid-polymer complexes and to the translation diffusion of BMIM cations in the matrix has been discussed.

Electrostatic Confinement‐Induced Excited Charge Transfer in Ionic Covalent Organic Framework Promoting CO2 Reduction

We demonstrate an electrostatic confinement‐induced charge transfer pathway in a supramolecular photocatalyst comprising of an ionic covalent organic framework (COF) and cationic metal complexes. The dynamic electrostatic interactions not only attract cations around the COF to accept photogenerated electrons, but also allows for a retention of homogeneous catalytic characters of complexes, making a subtle balance. Accordingly, the electrostatic confinement effect facilitates the forward electron transfer from a photoexcited COF to cationic Co complex, realizing a remarkable photocatalytic CO2 reduction performance. Its catalytic efficiency is far superior to the supramolecular counterparts with Van‐der‐Waals or hydrogen bonding interactions. This work presents an insight for enhancing charge transfer in supramolecular systems, and provides an effective approach for construction of highly efficient photocatalysts.

Guanidinium‐Based Covalent Organic Framework Membranes for Superior Mono‐ and Divalent Cations Separation

Biological membranes exhibit extraordinary efficiency in processing ion permeability and selectivity. However, creating artificial membranes for an ideal ion separation is still challenging due to the subtle distinctions in valence and size among different ions. In the realm of biological recognition, the ultimate selectivity of ion channels is considered to stem from the specific binding interactions and appropriate charge density. Designing artificial membranes to achieve similar performance not only helps the understanding of complex ion transport in bioprocesses but also facilitates critical industrial separations. Inspiring by the remarkable performance in biological systems, a guanidinium‐based covalent organic framework membrane is designed, which exhibits an excellent capability to recognize mono‐/divalent cations, achieving K+/Mg2+ selectivity up to 202 in a mixed salt solution. Furthermore, the membrane displays rapid ion transport owing to the uniform sub‐2 nm channels. The experimental results and molecular dynamics simulations illustrate that the charge‐assisted hydrogen bonding sites and the Cl− counter ions within 1D channels play critical roles in cations sieving. Specifically, divalent ions passing through the positively charged channels need to overcome higher energy barriers than monovalent ions. These findings offer promising avenues for the development of advanced multifunctional membranes for efficient ion separation and sustainable water‐related separations.

Complex Coacervates: From Polyelectrolyte Solutions to Multifunctional Hydrogels for Bioinspired Crystallization

Hydrogels represent multifarious functional materials due to their diverse ranges of applicability and physicochemical properties. The complex coacervation of polyacrylate and calcium ions or polyamines with phosphates has been uncovered to be a fascinating approach to synthesizing of multifunctional physically crosslinked hydrogels. To obtain this wide range of properties, the synthesis pathway is of great importance. For this purpose, we investigated the entire mechanism of calcium/polyacrylate, as well as phosphate/polyamine coacervation, starting from early dynamic ion complexation by the polymers, through the determination of the phase boundary and droplet formation, up to the growth and formation of thermodynamically stable macroscopic coacervate hydrogels. By varying the synthesis procedure, injectable hydrogels, as well as plastic coacervates, are presented, which cover a viscosity range of three orders of magnitude. Furthermore, the high calcium content of the calcium/polyacrylate coacervate (~19 wt.%) enables the usage of those coacervates as an ions reservoir for the formation of amorphous and crystalline calcium-containing salts like calcium carbonates and calcium phosphates. The exceptional properties of the coacervates obtained here, such as thermodynamic stability, viscosity/plasticity, resistance to acids, and adhesive strength, combined with the straightforward synthesis and the character of an ions reservoir, open a promising field of bioinspired composite materials for osteology and dentistry.

Five novel Pb/Zn/Co metal-organic frameworks using 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene and carboxylate ligands: Synthesis, characterization, DFT calculation and catalytic PMS degradation of RhB

Five new metal-organic frameworks (MOFs), namely {Pb(atpt)(3-bpd)0.5}n (1); {Co(cbz)2(3-bpd)(H2O)2·2H2O}n (2); {Co(imdc)(3-bpd)(H2O)·H2O}n (3); {Co(tdca)(3-bpd)(H2O)2·DMF}n (4); {Zn(tdca)(3-bpd)(H2O)2·DMF}n (5), were assembled with metal ions Pb²⁺, Zn²⁺, and Co²⁺ using 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene (3-bpd) as the main ligand, combined with 2-aminoterephthalic acid (H2atpt), 4-cyanobenzoic acid (Hcbz), 4,5-imidazoledicarboxylic acid (H2imdc), and thiophene-2,5-dicarboxylic acid (H2tdca) as auxiliary ligands via hydro/solvothermal methods. Their molecular structures were analyzed by single-crystal X-ray diffraction and characterized by FT-IR and PXRD. Complex 1 has a three-dimensional structure with a hepta-coordinated, semi-directed {PbNO6} metal center. The central metal ions in complexes 2–5 exhibit a six-coordinated {MN2O4} (M = Co or Zn) octahedral geometry. In complex 2, the carboxylate ligand does not function as a bridging ligand, resulting in a 1D chain structure, while complexes 3- 5 extend into 2D layered structures. Thermogravimetric analysis indicates good thermal stability for complexes 1–5. Then, the prepared complexes were used as catalysts to degrade Rhodamine B (RhB) during the monopersulfate (PMS) activation. Complexes 3 and 4 demonstrated significant efficiency, achieving degradation rates of 93.61 % and 98.56 % within 10 min. Radical scavenging experiments and EPR analysis identified that the activation of PMS for dye degradation by the two catalysts occurs through both radical and non-radical pathways, with SO4•− and •OH radicals being the dominant species. Density functional theory (DFT) calculations explained the superior catalytic performance of complex 4 compared to complex 3.

A gated highly variable pseudocapacitor based on redox-window control (G-CAPode)

Iontronic architectures operate via multiple ions or redox processes mimicking neural systems capable to operate with complex ions and biological transmitters with high energy efficiency. Recently, ultracapacitors have emerged as novel iontronic switchable devices with a high on/off ratio. We propose a novel iontronic device offering flexible control of the current output of a switchable electrochemical capacitor diode (CAPode) by introducing an additional "gate" electrode. This device mimics field-effect transistor (FET) semiconductors in controlling current output and recovers energy consumed during the forward charging, marking a significant breakthrough. A recently developed unidirectional CAPode system (Ni3Bi2S2@Ni I 1 mol L-1 KOH I AC@Ni) serves as the “working” capacitor (W-Cap) in the novel architecture. The proposed G-CAPode (gate-controlled CAPode) features a third voltage-controlled connection between the “gate” and the counter electrode of the W-Cap. By varying this third voltage channel the electrodes of W-Cap are shifted in potential toward negative or positive potential windows. Hence, by external voltage control the rectification ratios and blocking efficacy can be tuned which is essential for fully controlling the output signal in logic gates. A new circuit monitors the current and potential distribution of the “NOT” gate: The G-CAPode system exhibits transistor-like characteristics with a -1.2 V bias. This investigation highlights the versatility of the G-CAPode system across applications where transistor-like behavior and accurate current regulation are beneficial, promising advancements in ionologic devices, sensors, and energy storage systems.

Enhanced removal of Fe, Cu, Ni, Pb, and Zn from acid mine drainage using food waste compost and its mechanisms

Heavy metals (HMs) in acid mine drainage (AMD) pose serious threats to aquatic life and soil. Biosorbents are promising materials to remove HMs from wastewater. Herein, food waste compost was used as a low-cost and sustainable biosorbent to remove Fe3+, Cu2+, Ni2+, Pb2+, and Zn2+ from an AMD and other model solutions with an initial pH of 2.24. Batch adsorption tests were conducted to systematically investigate the influences of initial pH, compost dose, the presence of Fe3+ and SO42− ions, and the pH-induced Fe precipitates on the removal performance. The involved removal mechanisms were explored by conducting stepwise precipitation tests, sequential extraction tests, and Fourier transform infrared spectroscopy (FTIR) characterization. It was found that the addition of the compost removed over 90% of Zn, Ni, Cu, and Pb at pH 5.80, 5.50, 4.50, and 3.00, respectively. At low compost doses, the presence of Fe3+ and SO42− ions hindered the removal since the competition effect of Fe3+ ion and lower absorbability of metal-sulfate complexes, respectively. Sequential extraction tests revealed that higher fractions of Fe, Cu, and Pb were strongly immobilized through complexation and precipitation relative to Ni and Zn. Additionally, the pH-induced Fe precipitates did not favor the removal of the HMs, probably due to the adsorption of organic components released from the compost. This study suggests that compost have the potential to remove HMs from acidic wastewater without pre-neutralization.

Boosting energy storage properties of BNT-based relaxor ferroelectric ceramics via (Zn1/3Nb2/3)4+ complex ion doping

Boosting energy storage properties of BNT-based relaxor ferroelectric ceramics via (Zn1/3Nb2/3)4+ complex ion doping

An Efficient Fluorescent Chemosensing Probe for Total Determination and Speciation of Ultra-Trace Levels of Mercury (II) Species in Water.

The current study reports a novel fluorescent chemosensor based on the tagging agent 4,5,6,7-tetrachloro-2',4',5',7'-tetraiodofluorescein (Rose Bengal, RB) for detection of trace levels of Hg2+in environmental water. The established probe has been based upon liquid-liquid extraction (LLE) of the developed ternary complex ion associate {[Hg (bpy)2]2+.[RB]2-} of Hg2+ -2,2- bipyridyl complex [Hg (bpy)2]2+ and RB at pH 9.0 onto chloroform and measuring the resulting fluorescence enhancement signal intensity at λex/em = 570/ (580-600) nm. The limits of detection (LOD) and quantification (LOQ) of for Hg2+ was calculated to be 6.06 and 20 nM with a linear dynamic range (LDR) of 0.02-20µM, respectively. The stability constant, stoichiometry, chemical equilibria, and the thermodynamic parameters (ΔH, ΔS, and ΔG) of the developed ion associate were evaluated and assigned. Student's t and F tests at 95% confidence were fruitfully used for validation of the proposed methodology for Hg2+ detection in water samples with the aid of inductively coupled plasma-optical emission spectrometry (ICP-OES). The established strategy was successfully applied for detection of trace levels of Hg2+ in water samples with acceptable results. The proposed probe was satisfactorily applied for total determination and speciation of Hg in various water samples. Integrating the functional chelating agent onto associate formation to improve the selectivity and sensing properties of the LLE combining sensing probe towards target analyte in water represent the main interest.

A sequential treatment strategy by copper ion-doped nanofiber dressing for highly efficient biofilm combating and rapid wound healing

Copper ions are considered as a promising alternative to combat infected wound and accelerate wound healing. However, exhibiting good antibiofilm activity meanwhile minimizing cell toxicity remains a great challenge. To address this issue, we provide a sequential treatment strategy to combat biofilm infected wound with low copper ion (Cu2+) release (as low as 1.2 μg·mL−1). Polydopamine (PDA) adherent copper ion complex is constructed on thermoplastic polyurethane (TPU) to develop the Cu2+@PTPU nanofibers. With the application of Cu2+@PTPU wound dressing, nitric oxide (NO) gas is released by catalyzing endogenous donor, thereby rapidly eliminating more than 90 % biofilm biomass. Subsequent moderate photothermal treatment (∼47℃) significantly enhanced bactericidal effect by deconstructing bacteria membrane. As a result, the biofilm infection was eradicated in only ∼ 6h, significantly more effective than existing methods (∼24 h). Additionally, Cu2+@PTPU dressing not only exhibits excellent cell compatibility, but also promotes wound healing. In vivo study demonstrates that it reduces the level of inflammatory responses by 104 % and increases angiogenesis capacity by 115 %, compared with untreated group, thereby narrowing the wound site area by 72 % at day 14 after treatment. Overall, the Cu2+@PTPU dressing and sequential treatment strategy provide quick, safe, yet efficacious biofilm combating outcomes and facilitates rapid wound healing.

Au Nanoparticles-Trisbipyridine Ruthenium(II) Nanoaggregates as Signal-Amplifying SERS Tags for Immunoassay of cTnI.

Acute myocardial infarction (AMI) is one of the leading causes of human mortality worldwide. In the early stages of AMI, the patient's electrocardiogram (ECG) may not change, so the fast, sensitive, and accurate detection of the specific biomarker of cardiac troponin I (cTnI) is of great importance in the early diagnosis of AMI. In this work, for the first time, electrostatic nanoaggregates of negatively charged Au nanoparticles and positively charged trisbipyridine ruthenium(II) ions (i.e., (-)AuNPs|[Ru(bpy)3]2+ ENAs) as novel and signal-amplifying surface-enhanced Raman scattering (SERS) tags were synthesized in an easy and rapid (<3 min) way and applied in the highly sensitive, rapid detection of cTnI in human serum by being combined with an immunochromatographic test strip (ICTS). The synthesized (-)AuNPs|[Ru(bpy)3]2+ ENAs exhibited strong SERS activity due to the multiple Raman-active units (three bpy ligands) carried by each [Ru(bpy)3]2+ complex ion and abundant hotspots in each SERS tag. The developed (-)AuNPs|[Ru(bpy)3]2+ ENAs-based SERS-ICTS has been validated to be applicable in detection of cTnI in human serum with excellent sensing performances, such as fast testing (5 min) and a low detection limit (60 pg/mL). It is envisioned that the developed (-)AuNPs|[Ru(bpy)3]2+ ENAs-based SERS-ICTS sensor may have promising applications in point of care testing of various biomarkers in clinic. Additionally, this work may inspire the finding and the application of new types of Raman reporter molecules based on high valent metal-multi ligand coordination compounds like [Ru(bpy)3]2+.

Adsorption characteristics and mechanism of novel ink melanin composite modified chitosan for Cd(II) in water

In this study, chitosan (CS), carboxymethyl chitosan (CMCS), and chitosan quaternary ammonium salt (HACC) were successfully loaded with ink melanin (ME) as efficient adsorbents for Cd(II) removal. The results of batch adsorption experiments and structural characterization showed that the modified CS loaded with ME improved the adsorption capacity of the composites for Cd(II). The pseudo-second-order kinetic and Langmuir equations were better suited to describe the batch adsorption experiments. The adsorption of Cd(II) was chemisorption with desirable adsorption effect when the concentration of the three composites was 0.5 mg/mL and the pH value was neutral. Among them, HACC-ME demonstrated remarkable Cd(II) adsorption performance (107.18 mg/g) and sustained an 85 % efficiency in Cd(II) removal over five adsorption-desorption cycles. Ion exchange, complexation, electrostatic attraction, and hydrophobic interaction were the primary mechanisms for Cd(II) removal. Overall, HACC-ME could be employed as a low-cost and highly efficient new natural adsorbent material for the removal of Cd(II) ions from wastewater. These findings illuminate pathways for the development of efficient and novel natural adsorbent materials for environmental cleanup purposes.

A Fluorescence Sensor Based on Biphenolic Backbone for Metal Ion Detection: Synthesis and Crystal Structure

2′-(hexyloxy)-[1,1′-biphenyl]-2-yl 5-(dimethylamino)naphthalene-1-sulfonate (KC1) was synthesized by using biphenol and dansyl chloride as starting materials. The KC1 was characterized via single X-ray diffraction, FTIR, HRMS and 1H and 13C-NMR. The KC1 indicates triclinic as P1 in the space group type. From the KC1, the biphenolic backbone structure is twisted at an angle of 54.48° due to connecting the dansyl unit and hexyl moiety. Upon the addition of the Fe3+ ion to the KC1 solution, the fluorescence emission at 585 nm of KC1 was quenched due to complexation between KC1 and the Fe3+ ion. The complexation ratio of KC1 and Fe3+ was determined to be a 1:1 formation via Job’s analysis. The Stern–Volmer constant (Ksv) calculated was 21,203 M−1 for the KC1 and the Fe3+ ion complex.

Differential Spatiotemporal Patterns of Major Ions and Dissolved Organic Carbon Variations from Non-Permafrost to Permafrost Arctic Basins: Insights from the Severnaya Dvina, Pechora and Taz Rivers

The Arctic river basins, among the most sensitive regions to climate warming, are experiencing rapid temperature rise and permafrost thawing that profoundly affect their hydrological and hydrochemical systems. However, our understanding of chemical export from Arctic basins to oceans remains limited due to scarce data, particularly in permafrost-dominated regions. This study examines the spatiotemporal variations and seasonal dynamics of major ions (Na+, K+, Mg2+, Ca2+, Cl−, SO42−) and dissolved organic carbon (DOC) concentrations across three river basins with varying permafrost extents: the Severnaya Dvina (2006–2008, 2012–2014), the Pechora (2016–2019) and the Taz Rivers (2016–2020). All the data were sourced from published Chemical Geological researches and were taken from Mendeley and PANGAEA datasets. Our results showed that DOC concentrations ranged from 1.75 to 26.40 mg/L, with the Severnaya Dvina River exhibiting the highest levels of DOC concentrations, alongside significantly elevated ion concentrations compared to the other two basins. A positive correlation was observed between DOC concentrations and river discharge, with peaks during the spring flood and summer baseflow due to leaching processes. The Severnaya Dvina and Pechora Rivers exhibited the highest DOC values during the spring flood, reaching 26.40 mg/L and 8.07 mg/L, respectively. In contrast, the Taz River had the highest runoff during the spring flood season, but the DOC concentration reached its highest value of 11.69 mg/L in the summer. Specifically, a 1% increase in river discharge corresponded to a 1.25% rise in DOC concentrations in the Severnaya Dvina River and a 1.04% increase in the Pechora River, while there was no significant correlation between runoff and DOC concentrations in the Taz River. Major ion concentrations demonstrated a negative correlation with river discharge, remaining relatively high during winter low-flow period. A robust power-law relationship between river discharge and concentration of DOC and major ions was observed, with distinct variations across the three river basins depending on permafrost extent. The Pechora and Taz Rivers, characterized by extensive permafrost, exhibited increasing trends in river discharge and DOC concentrations, accompanied by decreasing major ion concentrations, whereas the non-permafrost-dominated Severnaya Dvina River basin showed the opposite pattern. The Taz River, with the most extensive permafrost, also displayed a delayed DOC peak and more complex seasonal ion concentration patterns. These findings highlight the importance of varying permafrost extents and their implications for water quality and environmental protection in these vulnerable regions.

Effect of binary ion substitution on the crystal structure and microwave dielectric properties of MgTa2O6 ceramics

AbstractMg1/3A11/3A21/3Ta2O6 ceramics (where A1 and A2 represent Co, Ni, or Zn) were prepared using the solid‐phase reaction route. The results of X‐ray diffraction and Raman tests showed that (Co1/2Ni1/2)2+, (Co1/ 2Zn1/2)2+, and (Ni1/2Zn1/2)2+ ions replaced Mg2+ ions in the lattice of MgTa2O6, resulting in the formation of a pure tri‐rutile structure. All three complex ions could significantly reduce the sintering temperature of the ceramics (by 150°C–200°C) and could broaden the sintering window. The large deviation (48.8%–69.2%) between the porosity corrected relative permittivity εr‐corr. and the theoretical relative permittivity εr‐theo. might be due to the overestimation of the ionic polarizability of Ta5+ by Shannon. (Co1/2Ni1/2)2+ has the most significant effect of increasing the bond energy of ceramic A–O bonds, reducing the τf value from 51 to 36 ppm/°C. In addition, the mechanisms affecting their dielectric properties are discussed based on bond ionicity (fi), full width at half maximum (FWHM) of Raman peak, and bond energy (E). Mg1/3Co1/3Ni1/3Ta2O6 ceramic sintered at 1350°C have the most excellent microwave dielectric properties: εr = 26.8, Q × f = 86,000 GHz, and τf = 36 ppm/°C.

Revealing the Reaction Pathway of Anodic Hydrogen Evolution at Magnesium Surfaces in Aqueous Electrolytes.

Aqueous metal corrosion is a major economic concern in modern society. A phenomenon that has puzzled generations of scientists in this field is the so-called anomalous hydrogen evolution: the violent dissolution of magnesium under electron-deficient (anodic) conditions, accompanied by strong hydrogen evolution and a key mechanism hampering Mg technology. Experimental studies have indicated the presence of univalent Mg+ in solution, but these findings have been largely ignored because they defy our common chemical understanding and evaded direct experimental observation. Using recent advances in the ab initio description of solid-liquid electrochemical interfaces under controlled potential conditions, we describe the full reaction path of Mg atom dissolution from a kinked Mg surface under anodic conditions. Our study reveals the formation of a solvated [Mg2+(OH)-]+ ion complex, challenging the conventional assumption of Mg2+ ion formation. This insight provides an intuitive explanation for the postulated presence of (Coulombically) univalent Mg+ ions, and the absence of protective oxide/hydroxide layers normally formed under anodic/oxidizing conditions. The discovery of this unexpected and unconventional reaction mechanism is crucial for identifying new strategies for corrosion prevention and can be transferred to other metals.

Spin-bearing molecules as optically addressable platforms for quantum technologies

Abstract Efforts to harness quantum hardware relying on quantum mechanical principles have been steadily progressing. The search for novel material platforms that could spur the progress by providing new functionalities for solving the outstanding technological problems is however still active. Any physical property presenting two distinct energy states that can be found in a long-lived superposition state can serve as a quantum bit (qubit), the basic information processing unit in quantum technologies. Molecular systems that can feature electron and/or nuclear spin states together with optical transitions are one of the material platforms that can serve as optically addressable qubits. The attractiveness of molecular systems for quantum technologies relies on the fact that molecular structures of atomically defined nature can be obtained in endless diversity of chemical compositions. Crucially, by harnessing the molecular design protocols, the optical and spin (electronic and nuclear) properties of molecules can be tailored, aiding the design of optically addressable spin qubits and quantum sensors. In this contribution, we present a concise and collective discussion of optically addressable spin-bearing molecules – namely, organic molecules, transition metal (TM) and rare-earth ion (REI) complexes – and highlight recent results such as chemical tuning of optical and electron spin quantum coherence, optical spin initialization and readout, intramolecular quantum teleportation, optical coherent storage, and photonic-enhanced optical addressing. We envision that optically addressable spin-carrying molecules could become a scalable building block of quantum hardware for applications in the fields of quantum sensing, quantum communication and quantum computing.