Metal-organic Complexes Research Articles

Intramolecular generation of endogenous Cu(III) for selectively self-catalytic degradation of Cu(II)-EDTA from wastewater by UV/peroxymonosulfate

HO•/SO4•−-based advanced oxidation processes for the decomplexation of heavy metal-organic complexes usually encounter poor efficiency in real scenarios. Herein, we reported an interesting self-catalyzed degradation of Cu(II)-EDTA with high selectivity in UV/peroxymonosulfate (PMS). Chemical probing experiments and competitive kinetic analysis quantitatively revealed the crucial role of in situ formed Cu(III). The Cu(III) species not only oxidized Cu(II)-EDTA rapidly at ∼3 × 107 M−1 s−1, but also exhibited 2–3 orders of magnitude higher steady-state concentration than HO•/SO4•−, leading to highly efficient and selective degradation of Cu(II)-EDTA even in complex matrices. The ternary Cu(II)-OOSO3- complexes derived from Cu(II)-EDTA decomposition could generate Cu(III) in situ via the Cu(II)-Cu(I)-Cu(III)-Cu(II) cycle involving intramolecular electron transfer. This method was also applicable to various Cu(II) complexes in real electroplating wastewater, demonstrating higher energy efficiency than commonly studied UV-based AOPs. This study provids a proof of concept for efficient decomplexation through activating complexed heavy metals into endogenous reactive species.

Electrochemical treatment of wastewaters containing metal-organic complexes: A one-step approach for efficient metal complex decomposition and selective metal recovery

Metal-organic complexes, especially those of ethylenediaminetetraacetic acid (EDTA) with metals such as copper (Cu) and nickel (Ni) (denoted here as Cu-EDTA and Ni-EDTA), are common contaminants in wastewaters from chemical and plating industries. In this study, a multi-electrode (ME) system using a two-chamber reactor and two pairs of electrodes is proposed for simultaneous electrochemical oxidation of a wastewater containing both Cu-EDTA and Ni-EDTA complexes as well as separation and selective recovery of Cu and Ni onto two different cathodes via electrodeposition. Our results demonstrate that the ME system successfully achieved 90% EDTA removal, 99% solid Cu recovery at the Cu recovery cathode and 56% Ni recovery (33.3% on the Ni recovery cathode and 22.6% in the solution) after a four-hour operation. The system further achieved 85.5% Ni recovery after consecutive five cycles of operation for 20 h. While Cu removal was mainly driven by the direct reduction of EDTA-complexed Cu(II) at the cathode, oxidation of EDTA within the Ni-EDTA complex at the anode was a prerequisite for Ni removal. The oxidation of metal-bound EDTA and free EDTA was driven by •OH and direct electron transfer on the PbO2 anode surface and graphite anode, respectively. We further show that ME system performs well for all pH conditions, treatment of real wastewaters as well as wastewaters containing other metals ions (Cr and Zn) along with Cu/Ni. The separation efficiency of Cu and Ni is dependent on applied electrode potential as well as nature and concentration of binding ligand present with comparatively lower separation efficiency achieved in the presence of weaker binding capacity and/or at lower ligand concentration and lower applied electrode potential. As such, some optimization of electrode potential is required depending on the nature/concentration of ligands in the wastewaters. Overall, this study provides new insights into the design and operation of EAOP technology for effective organic abatement and metal recovery from wastewaters containing mixtures of various metal-organic complexes.

Halogen Bond Catalysis: A Physical Chemistry Perspective.

As important noncovalent interactions, halogen bonds have been widely used in material science, supramolecular chemistry, medicinal chemistry, organocatalysis, and other fields. In the past 15 years, halogen bond catalysis has become a developed field in organocatalysis for the catalysts' advantages of being environmentally friendly, inexpensive, and recyclable. Halogen bonds can induce various organic reactions, and halogen bond catalysis has become a powerful alternative to the fully explored hydrogen bond catalysis. From a physical chemistry view, this perspective provides an overview of the latest progress and key examples of halogen bond catalysis via activation of the lone pair systems of organic functional group, π systems, and metal complexes. The research progresses in halogen bond catalysis by our group were also introduced.

Enhancing Cu-EDTA decomplexation in a discharge plasma system coupled with nanospace confined iron oxide: Insights into electron transfer and high-valent iron species

Decomplexation of heavy metal-organic complexes dominated by reactive oxygen species (ROS) oxidation had attracted extensive attention. Nanospace confinement is a novel strategy to enhance pollutant removal due to its regulation on ROS transformation and local accelerated dynamics. Herein, nano-confined Fe2O3 catalyst supported by carbon nanotubes (Fe2O3-in-CNTs) was synthesized, and it displayed obvious synergistic effects on decomplexation of Cu-EDTA complex in a non-thermal plasma (NTP) process. Cu-EDTA decomplexation efficiency reached 98.8% within 20 min in the NTP/Fe2O3-in-CNTs system, and the corresponding kinetic constant was 4.5 and 2.5 times as that in single NTP and unconfined systems, respectively. Based on experimental and theoretical results, nanospace confinement induced electron localization around Fe and C atoms and rearrangement of orbital electrons, favoring strongly oxidative FeⅣ formation and catalytic decomposition of H2O2 and O3. Nanospace confinement made Cu-EDTA decomplexation process transform from radical pathway to non-radical pathway. Cu-EDTA decomplexation pathways in the NTP/Fe2O3-in-CNTs were proposed.

Naphthalene Diimide-Tetraazacycloalkane Conjugates Are G-Quadruplex-Based HIV-1 Inhibitors with a Dual Mode of Action.

Human immunodeficiency virus 1 (HIV-1) therapeutic regimens consist of three or more drugs targeting different steps of the viral life cycle to limit the emergence of viral resistance. In line with the multitargeting strategy, here we conjugated a naphthalene diimide (NDI) moiety with a tetraazacycloalkane to obtain novel naphthalene diimide (NDI)-tetraazacycloalkane conjugates. The NDI inhibits the HIV-1 promoter activity by binding to LTR G-quadruplexes, and the tetraazacycloalkane mimics AMD3100, which blocks HIV entry into cells by interfering with the CXCR4 coreceptor. We synthesized, purified, and tested the metal-free NDI-tetraazacycloalkane conjugate and the two derived metal-organic complexes (MOCs) that incorporate Cu2+ and Zn2+. The NDI-MOCs showed enhanced binding to LTR G4s as assessed by FRET and CD assays in vitro. They also showed enhanced activity in cells where they dose-dependently reduced LTR promoter activity and inhibited viral entry only of the HIV-1 strain that exploited the CXCR4 coreceptor. The time of addition assay confirmed the dual targeting at the different HIV-1 steps. Our results indicate that the NDI-MOC conjugates can simultaneously inhibit viral entry, by targeting the CXCR4 coreceptor, and LTR promoter activity, by stabilizing the LTR G-quadruplexes. The approach of combining multiple targets in a single compound may streamline treatment regimens and improve the overall patient outcomes.

Photo-Controllable Ultralong Room-Temperature Phosphorescence: State of the Art.

In this concept, we showcase the upsurge in the studies of dynamic ultralong room-temperature phosphorescence (RTP) materials containing inorganic and/or organic components as versatile photo-responsive platforms. The goal is to provide a comprehensive analysis of photo-controllable RTP, and meanwhile delve into the underlying RTP properties of various classes of photochromic materials including metal-organic complexes, organic-inorganic co-crystals, purely organic small molecules and organic polymers. In particular, the design principles governing the integration of the photochromic and RTP moieties within a single material system, and the tuning of dynamic RTP in response to light are emphasized. As such, this concept sheds light on the challenges and opportunities of using these tunable RTP materials for potential applications in optoelectronics, particularly highlighting their use of reversible information encryption, erasable light printing and rewritable smart paper.

Metal-organic complex coating for enhanced corrosion control and biocompatibility on biodegradable magnesium alloy for orthopaedic implants.

Magnesium alloy is currently regarded as the most favourable biodegradable metal; however, obstacles remain to be overcome in terms of managing its corrosion and ensuring its biocompatibility. In this study, a metal-organic complex comprising Ca ions incorporated in tannic acid (TA) was prepared and used to coat magnesium alloy by chemical conversion and dipping processes, followed by modification with stearic acid (SA). This metal-organic complex coating was demonstrated to be homogeneous and compact, and it significantly improved the electrochemical corrosion resistance and long-term degradation behaviour of the coated samples. Consequently, the well-controlled release of Mg and Ca ions, as well as the osteo-compatible TA and SA molecules, promoted the proliferation of osteoblast cells. This metal-organic complex coating offers a promising modifying strategy for magnesium-based orthopaedic implants.

Optimal density-functional theory method for zinc-amino acid complexes determined by analyzing structural and Fourier-transform infrared spectroscopy data.

Metal-amino acid complexes are important compounds for the human body. Their nutritional value and anticancer, antibacterial, and catalytic properties are the focus of several studies. Density functional theory (DFT) can be used to predict their properties by optimizing their structures and performing electron population analyses. However, conventional computational methods cannot adequately determine the parameters of polymeric metal-amino acid complexes. Therefore, intermolecular interactions of polymers must be considered to correctly predict the properties of metal-amino acid and related metal complexes. In this study, different DFT protocols were used to acquire the infrared spectra and determine interatomic distances of two zinc-amino acid complexes, Zn(Gly)2 and Zn(Met)2. The results were compared to spectroscopic and X-ray crystallographic data, revealing that the M06 and M06-L functionals and the 6-311++G(d,p) basis set produced the smallest computational errors. Our results provide a foundation for future theoretical studies on other metal-amino acid and metal-organic complexes.

Synergistic effects of the substrate-ligand interaction in metal-organic complexes on the de-electronation kinetics of a vitamin C fuel cell.

The rising demand for portable energy conversion devices has spurred the advancement of direct liquid fuel cells (DLFCs) employing fuels such as alcohol, ammonia, hydrazine, and vitamin C. In these devices, various precious metal platforms have been explored to increase the de-electronation kinetics and reduce catalyst poisoning, but with substantial cost implications. We demonstrate the crucial role of ligands in non-precious organometallic complexes in influencing the de-electronation kinetics of fuel molecules through a unique substrate-ligand synergistic interaction. This unique chemistry imparts electron deficiency at the catalytic metal center while simultaneously populating the ligand with an extensive proton charge assembly. This distinct substrate-ligand interaction enhances the DLFC performance by coulombically dragging the substrate with a distinct amplification in its de-electronation kinetics. By integrating this approach with a ferricyanide/ferrocyanide half-cell reaction, a precious metal-free vitamin C fuel cell is developed, which is capable of generating an open circuit voltage of ∼950 mV, a peak power density of ∼97 mW cm-2 at a peak current density of ∼215 mA cm-2 with the performance metrics nearly 1.7 times higher than a precious metal based DLFC. This highlights the potential of the substrate-ligand synergy in the design of efficient molecular catalysts for energy conversion applications.

Hot carrier dynamics in metalated porphyrin-naphthalimide thin films.

This study employs femtosecond transient absorption spectroscopy to investigate the rapid dynamics of excited state carriers in three metalated porphyrin-naphthalimide (PN) molecules and one free-base molecule. The dynamics of electron injection, from PN to mesoporous titania (TiO2), in PN adsorbed TiO2 films (Ti-PN), were carefully investigated and compared to PN adsorbed ZrO2 films (Zr-PN). In addition, we examined the self-assembled PN films and found that, in their self-assembled state, these molecules exhibited a longer relaxation time than Zr-PN monomeric films, where the charge injection channel was insignificant. The ground-state bleach band in the Ti-PN films gradually shifted to longer wavelengths, indicating the occurrence of the Stark effect. Faster electron injection was observed for the metalated PN systems and the electron injection times from the various excited states to the conduction band of TiO2 (CB-TiO2) were obtained from the target model analysis of the transient absorption spectra data matrix. In these metal-organic complexes, hot electron injection from PN to CB-TiO2 occurred on a time scale of <360 fs. Importantly, Cu(II)-based PN complexes exhibited faster injection and longer recombination times. The injection times have been estimated to result from a locally excited state at ≈280 fs, a hot singlet excited state at 4.95 ps, and a vibrationally relaxed singlet excited state at 97.88 ps. The critical photophysical and charge injection processes seen here provide the potential for exploring the underlying factors involved and how they correlate with photocatalytic performance.

Discarding metal incorporation in pyrazole macrocycles and the role of the substrate on single-layer assemblies.

Pyrazole derivatives are key in crystal engineering and liquid crystal fields and thrive in agriculture, pharmaceutical, or biomedicine industries. Such versatility relies in their supramolecular bond adaptability when forming hydrogen bonds or metal-pyrazole complexes. Interestingly, the precise structure of pyrazole-based macrocycles forming widespread porous structures is still unsolved. We bring insight into such fundamental question by studying the self-assembled structures of a bis-pyrazole derivative sublimed in ultra-high-vacuum conditions (without solvents) onto the three (111) noble metal surfaces. By means of high-resolution scanning tunneling microscopy that is validated by gas phase density functional theory calculations, we find a common hexagonal nanoporous network condensed by triple hydrogen bonds at the molecule-metal interface. Such assembly is disrupted and divergent after annealing: (i) on copper, the molecular integrity is compromised leading to structural chaos, (ii) on silver, an incommensurate new oblique structure requiring molecular deprotonation is found and, (iii) on gold, metal-organic complexes are promoted yielding irregular chain structures. Our findings confirm the critical role of these metals on the different pyrazole nanoporous structure formation, discarding their preference for metal incorporation into the connecting nodes whenever there is no solvent involved.

Improved capacitive performances and electrocatalytic reduction activity by regulating the bonding interaction between Zn-bistriazole-pyrazine/pyridine units and diverse Anderson-type polyoxometalates.

Electrochemical performances can be effectively improved by introducing metal-organic units (MOUs) into polyoxometalates (POMs). However, regulating the bonding strength between POMs and MOUs at the molecular level to improve the electrochemical performance is a challenging task. Three new POM-based metal-organic complexes (MOCs), namely H{Zn2(Hpytty)2(H2O)8[CrMo6(OH)6O18]}·2H2O (1), H{Zn2(Hpyttz)2(H2O)6[CrMo6(OH)6O18]}·8H2O (2), and {(μ2-OH)2Zn6(pyttz)2(H2O)10[TeMo6O24]}·2H2O (3) (H2pytty = 3-(pyrazin-2-yl)-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl, H2pyttz = 3-(pyrid-2-yl)-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl), were obtained. Single-crystal X-ray diffraction shows that the bonding strength (from the hydrogen bond to the coordination bond) between Zn-bistriazole-pyrazine/pyridine units and diverse Anderson-type POMs gradually increases from complexes 1 to 3. Glassy carbon electrodes modified with complex 3 (3-GCE) has the highest specific capacitance, which is 930 F g-1 at 1 A g-1. Moreover, carbon paste electrodes (1-3-CPEs) modified with complexes 1-3 are used as electrochemical sensors for detecting Cr(VI) ions, with limits of detection well below the World Health Organization (WHO) maximum level in drinking water.

Aggregation-induced emission luminogens for latent fingerprint detection.

For over a century, fingerprints have served as a pivotal tool for identification of individuals owing to their enduring characteristics and easily apparent features, particularly in the realm of criminal investigations. Latent fingerprints (LFPs) are "invisible fingerprints" that are most commonly available at crime scenes and require a rapid, selective, sensitive, and convenient method for detection. However, existing fingerprint development techniques harbour limitations, prompting the exploration of novel approaches that prioritize investigator safety and environmental sustainability. Leveraging the unique photophysical properties of aggregation-induced emission luminogens (AIEgens) has emerged as a promising strategy for on-site analysis of LFP visualization. In this highlight, we have presented a comparative analysis of various AIEgens (organic compounds, metal complexes, nanoparticles, and polymers) for the development and detection of LFPs. Through this examination, insights into the efficiency and potential applications of AIE-based fingerprint development techniques are provided. In addition, several strategies have been proposed for circumventing the limitations of existing AIEgens. We hope that this highlight article will encourage more researchers to investigate AIEgens in LFP detection, contributing to forensic science.

Structural, optical and magnetic properties of a new metal-organic CoII-based complex.

A mononuclear cobalt(ii) complex [C5H8N3]2[CoCl4(C5H7N3)2] (I) was synthesized and structurally characterized. Single crystal X-ray diffraction analysis indicates that monometallic Co(ii) ions acted as coordination nodes in a distorted octahedral geometry, giving rise to a supramolecular architecture. The latter is made up of a ½ unit form composed of an anionic element [Co0.5Cl2(C5H7N3)]- and one 2-amino-4-methylpyrimidinium cation [C5H8N3]+. The crystalline arrangement of this compound adopts the sandwich form where inorganic parts are sandwiched between the organic sheets following the [100] direction. More information regarding the structure hierarchy has been supplied based on Hirshfeld surface analysis; the X⋯H (X = N, Cl) interactions play a crucial role in stabilizing the self-assembly process of I, complemented by the intervention of π⋯π electrostatic interaction created between organic entities. Thermal analyses were carried out to study the thermal behavior process. Static magnetic measurements and ab initio calculations of compound I revealed the easy-axis anisotropy character of the central Co(ii) ion. Two-channel field-induced slow-magnetic relaxation was observed; the high-frequency channel is characterized by underbarrier relaxation with U eff = 16.5 cm-1, and the low-frequency channel involves a direct relaxation process affected by the phonon-bottleneck effect.

Two new 6-nitrobenzimidazole ligand-modified polymolybdate-based metal–organic complexes with excellent capacitive and electrocatalytic performances

6-Nitrobenzimidazole ligand was first introduced into polyoxometalate-based metal–organic architecture, and two unique butterfly-like complexes were obtained. Their applications in electrochemical energy storage and electrocatalysis were studied.

Synthesis, characterization, and bioactivity evaluation of several divalent transition metal ion-bioflavonoid complexes

Interest in organic polyphenol compounds increases if these natural compounds are coordinated with transition metal ions. In this study, four metal complexes were synthesized with flavonoid extracts, and reliable techniques were used for characterization. These complexes showcase unique coloring, low pH, and conductivity levels, with X-ray diffraction revealing varying crystallinity among flavonoid extracts and certain complexes. Fourier transform infrared spectrophotometer exhibits a specific stretching vibration (442–486 cm−1 ν M−O), indicating flavonoid metal complex formation formation. UV–visible spectrum of flavonoid extracts displays absorption bands at 280 and 340 nm, shifting upon metal ion binding to unveil new absorption bands for each complex, producing three peaks between 260–660 nm. The 1HNMR results showed that the proton signals in all complexes shifted to a high field relative to their ligand, possibly due to increased coupling caused by the coordination effect and thus increased planarity of the flavonoid molecules. These organic metal complexes display heightened antioxidant, antimicrobial, and anticancer properties compared to extracts, with enhanced cytotoxicity against THP-1 and Calu-3 cell lines, notably Cu(II) displaying superior cytotoxic effects with IC50 values of 18 and 56 μg/mL for THP-1 and Calu-3 cells respectively.

Copper-containing POM-based hybrid P2Mo22V4Cu4 nanocluster as heterogeneous catalyst for the light-driven hydroxylation of benzene to phenol.

The current traditional phenol production process has many shortcomings, and the efficient and clean photocatalytic one-step oxidation to phenol is gradually attracting attention. Heteropolyacids (PMo10V2) with high-density Lewis acid active sites and excellent photoelectron transfer ability are ideal choices for catalytic reactions. In this study, a copper-modified isolated dimeric hybrid nanocluster, [Cu(pyim)2]2[Cu(pyim)2(P2MoVI20MoV2VIV4O82)]2·(H2O) (pyim = [2-(pyridin-2-yl)imidazole]), was synthesized by a convenient hydrothermal method. The structural analysis demonstrated that the compound was composed of metal-organic complexes containing pyim ligands, Keggin-type heteropolyacids, and transition metal copper ions. Remarkably, this not only solves the difficulty that the heteropolymeric acid cannot be recovered by dissolving in the solvent but also introduces the copper atom as a second active center. The catalyst exhibited a benzene conversion of 15.6% and a selectivity of 85.2% in a mixed solution of acetonitrile and acetic acid under optimal reaction conditions. After four catalytic cycles, the PXRD pattern proved that the catalyst was still stable. This study provides a good idea for photocatalytic reactions and other environmental applications.

N2H4Zn(HC3N3O3): exceptionally strong second harmonic generation and ultra-long phosphorescence.

The discovery and designed synthesis of multifunctional materials is a leading pursuit in materials science. Herein, we report a novel hydro-isocyanurate, N2H4Zn(HC3N3O3), which combines strong second harmonic generation (SHG) and ultra-long room-temperature phosphorescence (RTP). The SHG intensity is the highest within the cyanurate system (13 × KDP), and RTP lifetime extends up to 448 ms, accompanied by a long-lasting afterglow visible to the naked eye for 1.2 s, surpassing most of the current metal-organic complexes. This advancement holds promise for the development of multifunctional optoelectronic devices, particularly leveraging second-harmonic generation (SHG) processes.

Monolayers of a thiacalix[3]pyridine-supported molybdenum(0) tricarbonyl complex on Au(111): characterisation with surface spectroscopy and scanning tunneling microscopy.

Deposition of dome-shaped metal-organic complexes on metallic surfaces to produce well-defined single site catalysts is a novel approach combining aspects of homogeneous and heterogeneous catalysis. In order to investigate the bonding of small molecules to such systems, a molybdenum(0) tricarbonyl complex supported by a thiacalix[3]pyridine is synthesized and deposited on Au(111) and Ag(111) surfaces by vacuum evaporation. The resulting mono- and submonolayers are investigated with surface spectroscopy and STM. All of these methods indicate a parallel orientation of the molybdenum complex with respect to the surface. The vibrational properties and frequency shifts of the adsorbed complexes with respect to the bulk are evaluated with the help of conventional IR and IRRA spectroscopy, coupled to DFT calculations. Compared to a similar Mo(0) tricarbonyl complex supported by an azacalixpyridine ligand, the title complex exhibits a higher stability in the bulk and adsorbed to surfaces which goes along with a lower reactivity towards oxygen.

Desulfurization of thiosemicarbazones: the role of metal ions and biological implications.

Thiosemicarbazones are biologically active substances whose structural formula is formed by an azomethine, an hydrazine, and a thioamide fragments, to generate a R2C=N-NR-C(=S)-NR2 backbone. These compounds often act as ligands to generate highly stable metal-organic complexes. In certain experimental conditions, however, thiosemicarbazones undergo reactions leading to the cleavage of the chain. Sometimes, the breakage involves desulfurization processes. The present work summarizes the different chemical factors that influence the desulfurization reactions of thiosemicarbazones, such as pH, the presence of oxidant reactants or the establishment of redox processes as those electrochemically induced, the effects of the solvent, the temperature, and the electromagnetic radiation. Many of these reactions require coordination of thiosemicarbazones to metal ions, even those present in the intracellular environment. The nature of the products generated in these reactions, their detection in vivo and in vitro, together with the relevance for the biological activity of these compounds, mainly as antineoplastic agents, is discussed.