Complexation Research Articles

Triscyanocorrole, the Newest and Most Intriguing Member of the C1-Substituted Corrole Family.

Considering the potential advantages of minimally sized corroles for diverse applications, this study reports a facile access to cyano-substituted derivatives via a rare CF3/CN conversion. Investigation of the fully characterized gallium, phosphorus, and cobalt complexes discloses multiple effects of the meso-nitrile groups attached to the macrocycle. This corrole appears to be the most electron poor derivative which comes into play in the redox potentials of the corresponding complexes. Compared to its precursor, both the absorption and emission are strongly red shifted and the fluorescence lifetime and quantum yield are much larger. The coordination chemistry is affected as well, by virtue of axial ligands being perpendicular rather than parallel relative to each other.

General and Modular Synthesis of Covalent Organic Cages for Efficient Molecular Recognition.

Cage-type structures based on coordination and dynamic covalent chemistry have the characteristics of facile and efficient preparation but poor stability. Chemically stable organic cages, generally involving fragment coupling and multi-step reactions, are relatively difficult to synthesize. Herein, we offer a general and modular strategy to customize covalent organic cages with diverse skeletons and sizes. First, one skeleton (S) module with three extension (E) modules and three reaction (R) modules are connected by one- or two-step coupling to get the triangular monomer bearing three reaction sites. Then one-pot Friedel-Crafts condensation of the monomer and linking module of paraformaldehyde produces the designed organic cages. The cage forming could be regulated by the geometrical configuration of monomeric blocks. The S-E-R angles in the monomer is crucial; only 120° (2,4-dimethoxyphen as reaction module) or 60° (2,5-dimethoxyphen as reaction module) angle between S-E-R successfully affords the resulting cages. By the rational design of the three modules, a series of organic cages have been constructed. In addition, the host-guest properties show that the representative cages could strongly encapsulate neutral aromatic diimide guests driven by solvophobic interactions in polar solvents, giving the highest association constant of (2.58±0.18)×105 M-1.

General and Modular Synthesis of Covalent Organic Cages for Efficient Molecular Recognition

AbstractCage‐type structures based on coordination and dynamic covalent chemistry have the characteristics of facile and efficient preparation but poor stability. Chemically stable organic cages, generally involving fragment coupling and multi‐step reactions, are relatively difficult to synthesize. Herein, we offer a general and modular strategy to customize covalent organic cages with diverse skeletons and sizes. First, one skeleton (S) module with three extension (E) modules and three reaction (R) modules are connected by one‐ or two‐step coupling to get the triangular monomer bearing three reaction sites. Then one‐pot Friedel‐Crafts condensation of the monomer and linking module of paraformaldehyde produces the designed organic cages. The cage forming could be regulated by the geometrical configuration of monomeric blocks. The S−E−R angles in the monomer is crucial; only 120° (2,4‐dimethoxyphen as reaction module) or 60° (2,5‐dimethoxyphen as reaction module) angle between S−E−R successfully affords the resulting cages. By the rational design of the three modules, a series of organic cages have been constructed. In addition, the host‐guest properties show that the representative cages could strongly encapsulate neutral aromatic diimide guests driven by solvophobic interactions in polar solvents, giving the highest association constant of (2.58±0.18)×105 M−1.

Chiral Organometallic Complexes Derived from Helicenic N-Heterocyclic Carbenes (NHCs): Design, Structural Diversity, and Chiroptical and Photophysical Properties.

ConspectusRecently, helicene derivatives have emerged as an important class of molecules with potential applications spanning over asymmetric catalysis, biological activity, magnetism, spin filtering, solar cells, and polymer science. To harness their full potential, especially as emissive components in circularly polarized organic light-emitting diodes (CP-OLEDs), generating structural chemical diversity and understanding the resulting photophysical and chiroptical properties are crucial. In this Account, we shed light on chemical engineering combining helicene and N-heterocyclic carbene (NHC) chemistries to create transition-metal complexes with unique architectures and describe their photophysical and chiroptical attributes. The σ-donating and π-accepting capabilities of the helically chiral π-conjugated NHCs endow the complexes with remarkable structural and electronic features. These characteristics manifest in phenomena such as chirality induction, very long-lived phosphorescence, and strong chiroptical signatures (electronic circular dichroism and circularly polarized luminescence).We describe the different classes of ligands primarily developed in our group by classifying them according to their connection between the helicenic moiety and the imidazole precursor. This connection is essential in determining the degree of π-conjugation and characterizing the emissive state. We comprehensively discuss 6-coordinate, 4-coordinate, and 2-coordinate complexes, delving into their structural nuances and examining how the interplay between metals and auxiliary ligands shapes their photophysical properties, with interpretations enriched by DFT calculations. Helicenes are known to promote intersystem crossing thanks to strong spin-orbit coupling, while metals offer robust frameworks leading to a variety of molecular architectures with specific topologies together with distinct excited-state properties. The electronic configurations and energy levels of the ligand and metal orbitals thus significantly modulate the photophysical and chiroptical behaviors of these complexes. In-depth analysis of chiroptical properties, notably electronic circular dichroism and circularly polarized luminescence, emphasizes the influence of different stereogenic elements on the chiroptical responses across various energy ranges with appealing "match-mismatch" effects. Finally, we describe future prospects of helicene NHCs, particularly in the context of emerging research on cost-effective and abundant transition metals for materials science and for photocatalysis. Indeed, the inherent long-lived MLCT, excited-state delocalization, structural rigidity, and intrinsic chirality of these complexes present intriguing avenues for future investigations.

Novel Silicate Platform as Weakly-Coordinating Anions for Diverse Organometallic and Electrochemical Applications.

Weakly-coordinating anions (WCAs) are employed in a wide range of applications, but limitations remain, including high reactivity, limited redox window, complicated synthesis, high cost, low solublity, and low structural tunabililty. Herein, we report a new class of WCA based onalkyl or aryl (R)substitutedsilicates bearingfluorinated pinacolate ligands,"[RSiF24]-".Anions bearing a variety of R groups were prepared, enabling facile tuning of sterics and solubility. A range of cations employed in chemical reactivity has been supported by these anions, including ether-free alkali cations, Ag+, Ph3C+, Fc+, [NiI(COD)2]+. [Pd(dppe)(NCMe)Me]+has been generated by salt metathesis or protonation of a metal-alkyl bond, showcasing the ability of theRSiF24-anions to support applications in coordination chemistry and catalysis. Electrochemical studies on the [Bu4N]+variant show an exceptionally wide stability window for theMeSiF24-anion of 7.5 V in MeCN. CV experiments demonstrate reversible Mg deposition and stripping.

Novel Silicate Platform as Weakly‐Coordinating Anions for Diverse Organometallic and Electrochemical Applications

Weakly‐coordinating anions (WCAs) are employed in a wide range of applications, but limitations remain, including high reactivity, limited redox window, complicated synthesis, high cost, low solublity, and low structural tunabililty. Herein, we report a new class of WCA based on alkyl or aryl (R) substituted silicates bearing fluorinated pinacolate ligands, "[RSiF24]‐". Anions bearing a variety of R groups were prepared, enabling facile tuning of sterics and solubility. A range of cations employed in chemical reactivity has been supported by these anions, including ether‐free alkali cations, Ag+, Ph3C+, Fc+, [NiI(COD)2]+. [Pd(dppe)(NCMe)Me]+ has been generated by salt metathesis or protonation of a metal‐alkyl bond, showcasing the ability of the RSiF24‐ anions to support applications in coordination chemistry and catalysis. Electrochemical studies on the [Bu4N]+ variant show an exceptionally wide stability window for the MeSiF24‐ anion of 7.5 V in MeCN. CV experiments demonstrate reversible Mg deposition and stripping.

The potential of alkaline tolerant microbial consortia for textile wastewater treatment under integrated anaerobic/aerobic conditions: Performance evaluation and microbial community analysis

Sequential anaerobic/aerobic (A/O) treatment conditions for textile wastewater (WW) are more effective than conventional biological treatment. Anaerobic treatment is essential because anaerobic microbes can first break down complex and recalcitrant compounds, which are difficult to degrade under aerobic conditions. The simpler, more degradable compounds are then further broken down by aerobic microbes. This study aimed to evaluate the performance of a sequential A/O treatment process using a pilot-scale reactor to treat real textile WW and to characterize reactor and inoculum microbial community structures. The reactors were inoculated with microbial consortia originating from a diverse alkaliphilic soda lake in the Ethiopian Rift Valley. The WW test parameters were used to evaluate the performance of the treatment process. At steady state, the removal efficiencies were 97 % for dye, 86 % for Chemical Oxygen Demand (COD), and 93 % for Total Kjeldahl Nitrogen (TKN). Amplicon sequencing revealed that Firmicutes, Proteobacteria, and Actinobacteria were the dominant phyla in all the samples. Uncategorized microorganisms, followed by Alkalibacterium, Bifidobacterium, and Clostridium were the most abundant taxon in all the samples. The microbial community detected during the treatment process was not abundant in the inoculum originating from Lake Chitu, suggesting that the communities likely originated from textile WW. The textile WW treated with the integrated A/O process effectively degraded dyes, and the inoculated microbes demonstrated resistance to the toxic chemical composition of the WW. The integrated treatment process, along with the alkaliphilic microbial consortia, has proven to be practical for treating textile WW, offering valuable insights for field-scale applications.

Supported Binuclear Gold Phosphine Complexes as CO Oxidation Catalysts: Insights into the Formation of Surface‐Stabilized Au Particles

Atomically precise gold phosphine complexes as precursors for supported Au catalysts tested in CO oxidation are presented. Using a variety of analytical techniques, including in situ and operando X‐ray absorption spectroscopy, it is discovered that minor changes in the ligand of the molecular complexes result in significantly different activation behaviors of supported Au catalysts under reaction conditions. When using [Au2(μ2‐POP)2]OTf2 (POP = tetraphenylphosphoxane) as single‐source precursor, an active supported oxidation catalyst in second light‐off is obtained, outperforming a commercial Au/TiO2 and a P‐free Au/Al2O3 reference catalyst. Conversely, using [Au2(μ2‐dppe)2]OTf2 (dppe = diphenylphosphinoethane) on alumina leads to a significant decrease in CO oxidation activity. This difference is attributed to the formation of P‐containing ligand residues on the support in the case of [Au2(μ2‐POP)2]OTf2/Al2O3, which enhances the thermal stability of the Au particles and affects the particle's electronic properties through charge transfer processes. This work provides insights into the dynamic ligand decomposition of molecular gold complexes under reaction conditions and demonstrates the delicate balance between the stabilization of Au particles, clusters, and complexes using ligands and the blocking of active sites. This knowledge will pave the way for the targeted use of molecular transition metal complexes as precursors in synthesizing surface‐stabilized nanoparticles.

A Convenient Approach for the Synthesis of Multidentate N-Heterocyclic Carbene Ligand Precursors.

Multidentate bis-NHCs ligands with various spacers are expected to combine the advantages of coordination chemistry and catalysis. These offer opportunities to construct various organometallic frameworks involving transition metals and main group elements. Therefore, developing a general procedure for synthesizing a variety of carbene salt precursors using a convenient technique is key in this context. The extended protocol of a solvent-free approach for synthesizing various bridged bis-imidazolium carbene salts, including tris and tetrakis-imidazolium precursors, is reported here. This method can be performed in the laboratory, leading to high yields (80-95%) and isolated as analytically pure, multigram, bench-stable compounds.

A tale of two old drugs tetracycline and salicylic acid with new perspectives—Coordination chemistry of their Co(II) and Ni(II) complexes, redox activity of Cu(II) complex, and molecular interactions

Extensive use of the broad-spectrum tetracycline antibiotics (TCs) has resulted their wide spread in the environment and drive new microecological balances, including the infamous antibiotic resistance. TCs require metal ions for their antibiotic activity and resistance via interactions with ribosome and tetracycline repressor TetR, respectively, at specific metal-binding sites. Moreover, the Lewis-acidic metal center(s) in metallo-TCs can interact with Lewis-basic moieties of many bioactive secondary metabolites, which in turn may alter their associated chemical equilibria and biological activities. Thus, it is ultimately important to reveal detailed coordination chemistry of metallo-TC complexes. Herein, we report (a) conclusive specific Co2+, Ni2+, and Cu2+-binding of TC revealed by paramagnetic 1H NMR, showing different conformations of the coordination and different metal-binding sites in solution and solid state, (b) significant metal-mediated activity of Cu-TC toward catechol oxidation with different mechanisms by air and H2O2 (i.e., mono- and di-nuclear pathways, respectively), (c) interactions of metallo-TCs with bioactive salicylic acid and its precursor benzoic acid, and (d) noticeable change of TC antibiotic activity by metal and salicylic acid. The results imply that TCs may play broad and versatile roles in maintaining certain equilibria in microecological environments in addition to their well-established antibiotic activity. We hope the results may foster further exploration of previously unknown metal-mediated activities of metallo-TC complexes and other metalloantibiotics.

Angiogenesis-osteogenesis coupling and anti-osteoclastogenesis zoledronate intermixed calcium silicate metal-organic/inorganic hybrid coating on biodegradable zinc-based intramedullary nails for osteoporotic fracture healing

Osteoporotic (OP) fractures remain a tough clinical challenge owing to their impaired healing outcome, which requires novel biomaterials with osteogenicity for effective healing. Metallic zinc (Zn) is attracting increasing attention for biodegradable intramedullary nails (IMNs) for OP fracture healing thanks to their comprehensive mechanical properties, biosafety, and bioactivity. However, the multiple biofunctions required for OP fracture healing have not been fully met by Zn. Herein, a zoledronate (ZA)-mediated calcium-zinc silicate (Ca(Zn)Si) metal-organic/inorganic hybrid coating was fabricated on Zn-based IMN by coordination chemistry driven via interactions between ZA and Ca2+/Zn2+ as well as in-situ directional growth of Ca(Zn)Si phase. The ZA&Ca(Zn)Si hybrid coating exhibited a homogeneous micro/nanostructure with a granular morphology, which prevented premature fracture failure of IMN in rat femur by ameliorating corrosion mode and decreasing degradation rate of the Zn matrix. More importantly, this hybrid coating enabled sustained release of Zn2+/Ca2+/Si4+ and ZA in the long term, achieving a remarkable effect on vascularized bone regeneration. The coated IMN enhanced angiogenesis–osteogenesis coupling through autocrine and paracrine effects between endothelial cells and bone marrow mesenchymal stem cells. Osteoclastogenesis was repressed by Zn2+ and ZA. This approach offers a new strategy for surface-engineering of biodegradable metals for bone fracture healing.

The effect of a new 3-hydroxypyridine derivative LHT-2-20 on free radical oxidation in experimental periodontitis

Aim. To study the effect of a new complex compound LHT-2-20 (2-ethyl-6-methyl-3-hydroxypyridine-2-(3benzoyl phenyl)-propanoate) on free radical oxidation in experimental periodontitis.Materials and methods. The experimental study was performed on 195 white mongrel mice weighing 19–23 g and 137 white mongrel rats weighing 180–220 g. The effect of a new complex compound LHT-2-20 (2-ethyl-6methyl-3-hydroxypyridine-2-(3-benzoyl phenyl)-propanoate) on the intensity of free radical oxidation and the local state of periodontal tissues during a course of intragastric administration was studied on the experimental model of periodontitis. Statistical processing of the results was carried out using the SPSS Statistics 20.0 software package with the analysis of variance (ANOVA) and the parametric Tukey’s test.Results. The LHT-2-20 compound reduced elevated levels of primary and secondary lipoperoxidation products (conjugated dienes, malondialdehyde in plasma and in erythrocytes during spontaneous and iron-induced oxidation) already at the early stages of the experiment, bringing the studied parameters closer to the reference values by the end of the course of treatment. The use of the compound LHT-2-20 contributed to an increase in the activity of the main antioxidant enzymes (catalase and superoxide dismutase), normalizing them to baseline values by the end of the experiment. With the correction of free radical processes, the use of LHT-2-20 limited the local inflammatory response in periodontal tissues, which was confirmed by a decrease in gingival edema and hyperemia, bleeding, depth of periodontal pockets, and tooth mobility.Conclusion. The results of this study confirm the anti-inflammatory potential of the compound and the multiplicity of its effects due to the impact on the mechanisms of oxidative stress. The expediency of further study of the drug is justified by the prospect of creating a new drug and its subsequent wide clinical application as part of the complex therapy of periodontal inflammation.

New Brønsted–Lowry acid Co(II) complexes: Synthesis, characterization, and investigation of electrochemical application for sensing of salbutamol

In recent years, the employment of transition metal complexes for working electrode surface modification for sensor fabrication has become an area of research direction. Based on this, in this study, three Co(II) complexes: Co(phen)Cl2 (CoC12H8N2Cl2) (C1), and Brønsted–Lowry acids Co(phen)(HTA)Cl (CoC16H13N2O6Cl)(C2), and Co(phen)(HTA)2 (CoC20H18N2O12)(C3) were synthesized and characterized using various techniques such as UV–Vis, FT-IR, ICP OES, TGA, DTA, pXRD as well as electrolytic conductivity, and acid-base property analysis. C and C3 were found polycrystalline whose size falls within the nano range of 50 and 51 nm, respectively. The synthesis was intended to get materials for voltammetrically modifying glassy carbon electrodes for the determination of salbutamol. Salbutamolis a short-acting β2adrenergic receptor agonist that is applied for opening the medium and large airways in the lungs and eventually treats asthma among other problems. The electrochemical application of the synthesized materials was studied by fabricating through electropolymerization of C1, C2, and C3 on glassy carbon electrodes. The poly(C1)/GCE, poly(C2)/GCE, and poly(C3)/GCE) revealed effective surface area is 0.174 cm2, 0.183 cm2, and 0.281 cm2, respectively, and electrochemical catalysis of the materials increased with the number of the tartrate. The Rct values are 5686, 242, 216, and 185 Ω cm2, while the Cdl values are 9.93 × 10−8, 5.35 × 10−6, 1.25 × 10−5, and 2.72 × 10−5, for bare GCE, poly(C1)/GCE, poly(C2)/GCE and poly(C3)/GCE, respectively. Similarly, the rate of charge transfer (k°) increased significantly on the modified electrode compared to the bare GCE. Salbutamol demonstrated a single well-shaped irreversible oxidative peak at the modified electrodes in the ascending order of poly(C1)/GCE, poly(C2)/GCE, and poly(C3)/GCE when compared to a bare GCE.

Research Progress of Deep-Red to Near-Infrared Electroluminescent Materials Based on Organic Cyclometallated Platinum(II) Complexes.

In recent years, the near-infrared (NIR) light-emitting materials have attracted increasing attention due to the broad application prospects in the fields of military industry, aerospace, lighting, display and wearable devices. As the transition metal complexes, platinum(II) complexes have been shown to emit luminescence efficiently in NIR organic light-emitting diodes because of the unique d8 electron structure. This structure ensures that the platinum(II) complex molecules exhibit a high planarity, variety of excited states, and strong intermolecular interactions. This review summarizes the research progress of deep red to NIR organic light-emitting materials based on platinum(II) complexes in recent years and provides a certain reference for the further design and synthesis of NIR platinum(II) complex luminescent materials with superior performance.

Biomineralized Nuclear Receptor Protein-Selection Mass Spectrometry for the Discovery of Drugs and Toxics.

Protein-selection mass spectrometry is cost-effective for the discovery of drugs and toxics. Nuclear receptors (NRs) are major targets for pharmaceuticals and endocrine-disrupting chemicals and are, thus, widely used as "bait" proteins. However, their application is limited due to the tendency to lose protein activity during cold storage. To address this problem, we introduced a novel biomineralization-based approach to preserve activity in NRs, exemplified by human retinoic acid receptor alpha (hRARα), a target for cancer and leucocythemia therapy. Since information on the coordination chemistry of metal ion and NR protein complexes is almost unavailable, we applied peptide mapping analysis for the first time for the rational design of his-hRARα-Co phosphate nanobiomaterial with high bioactivity. This nanobiomaterial successfully captured hRARα bioactive chemicals from a Chinese herb and environmental water and discovered an unsaturated fatty acid, (±)-(9Z,11E)-13-hydroxy-9,11-octadecadienoic acid ((±)13-HODE), which exhibited strong hRARα antagonistic activity.

Affecting Charges and Structures of {Bi6} Architectures by 12‐Electron Transition Metal Fragments

Molecules based on polyatomic bismuth substructures are currently attracting a lot of attention owing to this heavy and essentially non‐toxic element’s uncommon chemical and physical properties, which include unprecedented bonding properties. Hexaatomic {Bi6} substructures that underly more complex cluster structures were recently reported to adopt different structures or exhibit different structural details as a consequence of the charge of the {Bi6} unit. This leads to either crown‐shaped cycles for a nominal Bi66− or differently distorted trigonal prisms for compositions close to Bi62−. It was predicted by quantum chemistry that Bi64− should adopt a distinctly distorted boat‐like shape, yet a corresponding compound has remained elusive. Here, we report a proof of this assumption by the synthesis and isolation of [K(crypt‐222)]2[Bi6{Zn(hmds)}2]∙1.5THF (1), comprising a bimetallic [Bi6{Zn(hmds)}2]2− cluster that fulfils the prediction for the geometric and electronic structure of the missing link (crypt‐222 = 4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo‐[8.8.8]hexa‐cosane, hmds = hexamethyldisilazanid). A detailed quantum chemical study shows how the nature of Lewis‐acidic transition metal complexes – in particular, 12‐electron fragments – control and fine‐tune the resulting {Bi6} architectures in accordance with the degree of electron‐withdrawal from the polybismuthide core.

Liquid Rocket Engine Performance Characterization Using Computational Modeling: Preliminary Analysis and Validation

The need to refuel future missions to Mars and the Moon via in situ resource utilization (ISRU) requires the development of LOX/LCH4 engines, which are complex and expensive to develop and improve. This paper discusses how the use of digital engineering—specifically physics-based modeling (PBM)—can aid in developing, testing, and validating a LOX/LCH4 engine. The model, which focuses on propulsion performance and heat transfer through the engine walls, was created using Siemens’ STAR-CCM+ CFD tool. Key features of the model include Eulerian multiphase physics (EMP), complex chemistry (CC) using the eddy dissipation concept (EDC), and segregated solid energy (SSE) for heat transfer. A comparison between the complete GRI 3.0 and Lu’s reduced combustion mechanisms was performed, with Lu’s mechanism being chosen for its cost-effectiveness and similar output to the GRI mechanism. The model’s geometry represents 1/8th of the engine’s volume, with a symmetric rotational boundary. The performance of this engine was investigated using NASA’s chemical equilibrium analysis (CEA) and STAR-CCM+ simulations, focusing on thrust levels of 125 lbf and 500 lbf. Discrepancies between theoretical predictions and simulations ranged from 1.4% to 28.5%, largely due to differences in modeling assumptions. While NASA CEA has a zero-dimensional, steady-state approach based on idealized conditions, STAR-CCM+ accounts for real-world factors such as multiphase flow, turbulence, and heat loss. For the 125 lbf case, a 9.2% deviation in combustion chamber temperature and a 15.0% difference in thrust were noted, with simulations yielding 113.48 lbf compared to the CEA’s 133.52 lbf. In the 500 lbf case, thrust reached 488 lbf, showing a 2.4% deviation from the design target and an 8.6% increase over CEA predictions. Temperature and pressure deviations were also observed, with the highest engine wall temperature at the nozzle throat. Monte Carlo simulations revealed that substituting LNG for LCH4 affects combustion dynamics. The findings emphasize the need for advanced modeling approaches to enhance the prediction accuracy of rocket engine performance, aiding in the development of digital twins for the CROME.

Affecting Charges and Structures of {Bi6} Architectures by 12-Electron Transition Metal Fragments.

Molecules based on polyatomic bismuth substructures are currently attracting a lot of attention owing to this heavy and essentially non-toxic element's uncommon chemical and physical properties, which include unprecedented bonding properties. Hexaatomic {Bi6} substructures that underly more complex cluster structures were recently reported to adopt different structures or exhibit different structural details as a consequence of the charge of the {Bi6} unit. This leads to either crown-shaped cycles for a nominal Bi66- or differently distorted trigonal prisms for compositions close to Bi62-. It was predicted by quantum chemistry that Bi64- should adopt a distinctly distorted boat-like shape, yet a corresponding compound has remained elusive. Here, we report a proof of this assumption by the synthesis and isolation of [K(crypt-222)]2[Bi6{Zn(hmds)}2]∙1.5THF (1), comprising a bimetallic [Bi6{Zn(hmds)}2]2- cluster that fulfils the prediction for the geometric and electronic structure of the missing link (crypt-222 = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-[8.8.8]hexa-cosane, hmds = hexamethyldisilazanid). A detailed quantum chemical study shows how the nature of Lewis-acidic transition metal complexes - in particular, 12-electron fragments - control and fine-tune the resulting {Bi6} architectures in accordance with the degree of electron-withdrawal from the polybismuthide core.

Metal-Ligand Covalency in the Valence Excited States of Metal Dithiolenes Revealed by S 1s3p Resonant Inelastic X-ray Scattering.

Metallo dithiolene complexes with biological and catalytic relevance are well-known for having strong metal-ligand covalency, which dictates their valence electronic structures. We present the resonant sulfur Kβ (1s3p) X-ray emission spectroscopy (XES) for a series of Ni and Cu bis(dithiolene) complexes to reveal the ligand sulfur contributions to both the occupied and unoccupied valence orbitals. While S K-edge X-ray absorption spectroscopy played a critical role in identifying the covalency of the unoccupied orbitals of metal dithiolenes, the present focus on XES explores the occupied density of states. For a series of [Cu(mnt)2]n- and [Ni(mnt)2]n- anions and dianions, a comparison of the nonresonant and resonant S Kβ XES spectra highlights the dramatic improvement in spectral resolution and corresponding ability to differentiate subtle changes in occupied electronic structure across the series. Furthermore, the use of resonant inelastic X-ray scattering (RIXS) probes the valence excited states and the core-valence couplings of the complexes. By employing a theoretical approach based on time-dependent density functional theory to interpret the RIXS spectra, we reveal how metal-ligand covalency influences the excited state energies and covalencies. We identify the low energy excited states as having the same symmetry as the nominal "ligand field" or "d-d" states that typically dominate the photophysics of 3d metal complexes but with significant metal-ligand charge transfer character dictated by their covalency. These results suggest that strong metal-ligand covalency can be used to influence the charge-transfer photochemistry of first row transition metal complexes.

Chemistry of Antimony in Radiopharmaceutical Development: Unlocking the Theranostic Potential of Sb Isotopes.

Antimony-119 (119Sb) holds promise for radiopharmaceutical therapy (RPT), emitting short-range Auger and conversion electrons that can deliver cytotoxic radiation on a cellular level. While it has high promise theoretically, experimental validation is necessary for 119Sb in vivo applications. Current 119Sb production and separation methods face robustness and compatibility challenges in radiopharmaceutical synthesis. Limited progress in chelator development hampers targeted experiments with 119Sb. This review compiles literature on the toxicological, biodistribution and redox properties of Sb, along with existing Sb complexes, evaluating their suitability for radiopharmaceuticals. Sb(III) is suggested as the preferred oxidation state for radiopharmaceutical elaboration due to its stability in vivo and lack of skeletal uptake. While Sb complexes with both hard and soft donor atoms can be achieved, Sb thiol complexes offer enhanced stability and compatibility with the desired Sb(III) oxidation state. For 119Sb to find application in RPT, scientists need to make discoveries and advancements in the areas of isotope production, and radiometal chelation. This review aims to guide future research towards harnessing the therapeutic potential of 119Sb in RPT.