Ligand Coordination Research Articles

Luminescence Thermochromism of a Noncluster Copper Iodide Complex.

Hybrid copper(I) halide materials are currently attracting significant attention due to their exceptional luminescence properties, offering great potential for the development of multifunctional emissive materials with, in addition, eco-friendly features. A binuclear copper iodide complex, based on the [Cu2I2L4] motif with phosphite derivatives as ligands, has been synthesized and structurally characterized. Photophysical investigations indicate that this complex displays luminescence thermochromic properties, which are characterized by a temperature-dependent change in the relative intensity of two emission bands. The high-contrast luminescence thermochromism, with an important color variation from purple to cyan, is ascribed to the thermal equilibrium of two different excited states. While thermochromism is relatively known for multimetallic complexes, the perfectly controlled thermochromism of the studied compound is unprecedented for a binuclear complex. From theoretical investigations, this original feature is due to the coordination of phosphite ligands, which induces a specific energy layout of the complex, presenting vacant orbitals of varying nature. This single-component, dual-emissive binuclear complex, displaying relevant sensitivity temperature response, presents great potential for luminescence ratiometric thermometry applications. This study underlines the relevance of the ligand engineering strategy in developing original, emissive, and sustainable copper-based materials.

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+.

Theoretical Investigation of Interconversion Pathways and Intermediates in Hydride/Silyl Exchange of Niobocene Hydride–Silyl Complexes: A DFT Study Incorporating Conformational Search and Interaction Region Indicator (IRI) Analysis

Niobocene hydride–silyl complexes exhibit intriguing structural characteristics with the potential for direct hydride/silyl exchange, where hydride migration plays a crucial role during conformational interconversion. In this study, quantum chemical calculations were utilized to investigate the transformation pathways involved in hydride/silyl exchange in niobocene trihydride complexes with various dichlorosilanes, including SiCl2Me2, SiCl2iPr2, and SiCl2MePh ligands. The conformational changes and hydride shifts within these niobocene hydride–silyl complexes were examined, and key intermediates were identified. Electronic wavefunction analysis provided insights into the coordination configurations and the nature of inter-ligand interactions. Interaction region indicator (IRI) analysis revealed Van der Waals interactions between chloride atoms and cyclopentadienyl rings, as well as between chloride atoms and Me, iPr, and Ph groups. Notably, distinct interactions between hydride ligands, including those from Si-H moieties and coordinated hydrogen atoms, were observed. Both lateral and central conformations, with respect to silicon coordination to the niobium center, were considered. This study enhances the understanding of intermediate conformations in the hydride/silyl exchange process and provides a detailed characterization of inter-ligand interactions, offering valuable insights for analyzing metallocene complexes with organic ligand coordination.

Examining the Influence of Silver(I) Ion Coordination Environment in Ionic Liquids on Olefin-Paraffin Separations using Inverse Gas Chromatography.

Silver(I) ions (Ag+) undergo selective π-complexation with olefins and have been employed as separation media for the isolation of olefins from structurally similar paraffins. Ionic liquids (ILs) possess minimal vapor pressures, exceptional thermal stabilities, low melting points, as well as provide a favorable environment for π-complexation between Ag+ ions and olefins. The development of molecular drivers capable of highly selective olefin/paraffin separation systems with Ag+-containing ILs necessitates a comprehensive understanding of all factors that affect olefin solubility and selectivity. This study examines how coordinating different ligand species to Ag+ ions produces separation media with varying interaction strengths to olefins. Four coordination compounds, (4,4'-dimethyl-2,2'-bipyridine)silver(I) bis[(trifluoromethyl)sulfonyl]imide ([Ag+(DMBP)][NTf2-]), bis(pyridine)silver(I) [NTf2-] ([Ag+(Py)2][NTf2-]), bis(2,6-lutidine)silver(I) [NTf2-] ([Ag+(Lut)2][NTf2-]), and (triphenylphosphine)silver(I) [NTf2-] ([Ag+(PPh3)][NTf2-]) were dissolved in the 1-decyl-3-methylimidazolium [NTf2-] ([DMIM+][NTf2-]) IL and employed as stationary phases for inverse gas chromatography. Ligand coordination to the Ag+ ion was observed to modulate interactions of unsaturated hydrocarbons. The [Ag+(Py)2][NTf2-] complex offered the greatest olefin retention among the coordination complexes reaching 54% of the 1-octene retention factor of the uncoordinated [Ag+][NTf2-]. Hydrogen (H2) exposure studies showed ligand-dependent rates of reduction from Ag+ ion to elemental silver (Ag0). The [Ag+(PPh3)][NTf2-] complex exhibited superior stability, compared to the neat [Ag+][NTf2-] salt, reducing the retention factor of 1-octene by 15.3% and 19.4%, respectively, after 200 h of H2 exposure at 70 °C. The results from this study show that coordination complexes with Ag+ ions are useful in highly selective and efficient petroleum processing systems.

Controllable Regulation of CO2 Adsorption Behavior via Precise Charge Donation Modulation for Highly Selective CO2 Electroreduction to Formic Acid.

The synthesis of value-added products via CO2 electroreduction (CO2ER) is of great significance, but the development of efficient and versatile strategies for the controllable selectivity tuning is extremely challenging. Herein, the tuning of CO2ER selectivity through the modulation of CO2 adsorption behavior is proposed. Using the constructed zeolitic MOF (SNNU-339), CO2 adsorption behavior is controllably changed from *CO2 to CO2* via the precise ligand-to-metal charge donation (LTMCD) regulation. It is confirmed that the high electronegativity of the coordinate ligand directly restricts the LTMCD, reduces the charge density on the metal sites, lowers the Gibbs free energy for CO2* adsorption, and leads to the transformation of CO2 adsorption mode from *CO2 to CO2*. Owing to the modulated CO2 adsorption behavior and regulated kinetics, SNNU-339 exhibits superior HCOOH selectivity (≈330% promotion, 85.6% Faradaic efficiency) and high CO2ER activity. The wide applicability of the proposed approach sheds light on the efficient CO2ER. This study provides a competitive strategy for rational catalyst design and underscores the significance of adsorption behavior tuning in electrocatalysis.

Excitation Dependent Multiemissive Behaviour of Triimidazole Carboxylic Acid anti‐Kasha Luminophore and its Mononuclear Metal Complexes

Materials based on small molecules characterized by multi‐component short and long‐lived emissive behaviour are extremely desirable for various applications. The derivative of cyclic triimidazole (TT) functionalized with a carboxylic group, namely TT‐COOH, is isolated, investigated and used as coordinative ligand to obtain a series of isomorphous mononuclear complexes of general formula [M(TT‐COO)2(H2O)2] (M = Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II)). Crystals of TT‐COOH display aggregation induced enhanced emission (AIEE) comprising dual fluorescence and dual phosphorescence of molecular origin together with an aggregation induced long lived, low energy phosphorescence. Emissive features are retained in crystals of the Zn(II) and Cd(II) complexes, where the metal plays the role of an external heavy atom perturber, but strongly quenched in the others. The mechanisms involved in the photophysics of TT‐COOH and its metal complexes have been disclosed thanks to combined structural, spectroscopic and computational investigations which reveal the presence of anti‐Kasha emissions.

Heterometallic-Organic Cages with Customized Cavities: Constructed by Bottom-Up Step-Wise Coordination-Driven Self-Assembly.

Accurately synthesizing coordination-driven metal-organic cages with customized shape and cavity remains a great challenge for chemists. In this work, a bottom-up step-wise coordination-driven self-assembly approach was put forward. Employing this strategy, three terpyridyl heterometallic-organic truncated tetrahedral cages with different sizes and cavity were precisely synthesized. Firstly, the coordination of tripodal organic ligands with Ru2+ afforded dendritic metal-organic ligands L1-L3. Then the Ru building blocks complexed with Fe2+ and shrunk to form the desired heterometallic-organic cages (C1-C3). These discrete heterometallic-organic supramolecular cages were fully characterized and displayed the large and open cavities varied from 7205 Å3 to 9384 Å3. Notably, these cages could not be directly constructed by single-step assembly process using initial organic ligands or dimeric metal-organic ligands, indicative of the irreplaceability of a bottom-up step-wise assembly strategy for size-customized architectures. This work paves a new way for precisely constructing metal-organic cages with well-defined cavities.

Attenuating Nucleophilicity of Titanocene Hydrides Beyond Steric Effects en Route to Fatty Alcohols.

Here, we introduce a new class of titanocene catalysts for epoxide hydrosilylation that frustrates their hydridicity and thereby emphasizes their electron transfer reactivity. This unique attenuation of hydridicity is accomplished by introducing Lewis acidic silicon centers to the cyclopentadienyl ligands for an intramolecular coordination of the titanium-bound hydride. The superiority of our rationally designed catalysts over classic titanocenes with alkyl-substituted cyclopentadienyl ligands is demonstrated in the dramatically improved regioselectivity of the hydrosilylation of monosubstituted epoxides to primary alcohols.

Synthesis and Photochemical Properties of Heterometallic Ti-Cu Ring Clusters Constructed from Myo-Inositol Ligand.

Incorporating heterometals into titanium-oxygen clusters represents an effective approach to adjusting the band gap and absorption properties. Herein, a family of heterometallic Ti-Cu clusters was synthesized under solvothermal conditions. The unique structural feature of these clusters is the formation of ring clusters with myo-inositol ligands serving as structure-directing ligands. The myo-inositol ligand, as a typical polyol ligand, demonstrates flexible and distinctive coordination modes capable of chelating up to eight transition metal ions simultaneously. Compounds 4 and 5 show significant absorption in the visible region, indicating that the incorporation of Cu ions can efficiently tune the band gap of titanium-oxygen clusters.

The chromatin remodeler SMARCA5 binds to d-block metal supports: Characterization of affinities by IMAC chromatography and QM analysis.

The ISWI family protein SMARCA5 contains the ATP-binding pocket that coordinates the catalytic Mg2+ ion and water molecules for ATP hydrolysis. In this study, we demonstrate that SMARCA5 can also possess an alternative metal-binding ability. First, we isolated SMARCA5 on the cobalt column (IMAC) to near homogeneity. Examination of the interactions of SMARCA5 with metal-chelating supports showed that, apart from Co2+, it binds to Cu2+, Zn2+ and Ni2+. The efficiency of the binding to the last-listed metal was influenced by the chelating ligand, resulting in a strong preference for Ni-NTA over the Ni-CM-Asp equivalent. To gain insight in the preferential affinity for the Ni-NTA ligand, QM calculations were performed on model systems and metal-ligand complexes with a limited protein fragment of SMARCA5 containing the double-histidine (dHis) motif. The calculations correlated the observed affinity with the relative stability of the d-block metals to tetradentate ligand coordination over tridentate, as well as their overall octahedral coordination capacity. Likewise, binding free energies derived from model imidazole complexes mirrored the observed Ni-NTA/Ni-CM-Asp preferential affinity. Finally, similar calculations on complexes with a SMARCA5 peptide fragment derived from the AlphaFold structural prediction, captured almost accurately the expected relative stability of the TM complexes, and produced a large energetic separation (~10 kcal∙mol-1) between Ni-NTA and Ni-CM-Asp in favour of the former.

Overcoming surface quenching in persistent luminescence nanoparticles with organic ligand coordination: Implications for enhanced optical imaging

Persistent luminescence nanoparticles (PLNPs) have been considered as excellent luminescent tools for sensitive optical imaging. However, the persistent luminescence (PL) properties of PLNPs are usually suppressed due to severe surface quenching caused by nanoscale size. Despite considerable efforts, the understanding of surface quenching mechanisms remains a challenge. Here we report a surface ligand coordination method to enhance the PL properties of ZnGa2O4:Al,Cr (ZGO:AC) PLNPs. ZGO:AC PLNPs coated with organic ligands containing carboxyl groups show enhanced PL intensity and prolonged decay time. Among the six ligands, the phthalic acid (PA) ligands yielded the largest luminescence enhancement effect, on which the PL intensity and decay time increased 3 and 2 times compared with ligand-free ZGO:AC PLNPs, respectively. Density functional theory (DFT) calculations and detailed characterizations demonstrated that surface quenching is suppressed due to the coordination of non-saturated Ga ions and -COO- of ligands. Finally, ZGO:AC@PA PLNPs were applied in autofluorescence-free bioimaging and exhibited high imaging sensitivity and contrast ratio. These findings provide insights into the surface quenching mechanisms of PLNPs and offer a platform for developing highly emissive PLNPs on nanoscale.

Single and mixed dithiocarbamato metal(III) complexes (Co, Rh, and Ir): Crystal and molecular structure description and interplay

This review focuses on the crystal and molecular structures of single and mixed dithiocarbamate ligands of cobalt, rhodium, and iridium in the +3 oxidation state. The complexities of their chelating and bridging modes come into play through modification of the substituents on the carbamate nitrogen atoms of the ligands and additional coordination of secondary phosphino-containing ligands, culminating in various applications such as biological, analytical, medicine, and catalysis. Other considerations include the geometrical coordination environments around the metal centres and their comparison with isostructural congeners. The distortions around the metal centres and their subsequent effects on the symmetries of bonds in the primary and secondary coordination spheres are discussed. The trans-effects of secondary P-ligands and their effects on geometrical alignment and structural stability have become valuable yardsticks in analyzing structural modifications and stabilities.

Synthesis, Structural Determination, DFT Calculation and Biological Evaluation Supported by Molecular Docking Approach of Some New Complexes Incorporating (E)‐N'‐(3,5‐di‐Tert‐Butyl‐2‐Hydroxybenzylidene) Isonicotino Hydrazide Ligand

ABSTRACTThe synthesis and structural analysis of complexes derived from (E)‐N′‐(3,5‐di‐tert‐butyl‐2‐hydroxybenzylidene) isonicotino hydrazide (ITB ligand) were examined using multiple analytical techniques. These techniques included TGA, decomposition point determination, elemental analysis (CHN), spectroscopic (IR, NMR, mass spectrometry) analysis, magnetic susceptibility, conductivity, as well UV–Vis spectrum analysis, along with theoretical studies. Molar conductance values indicated that the Cd (II), Co (II), Cu (II), Ni (II), and Zn (II) complexes are non‐electrolytes in fresh DMSO solutions, with conductance values ranging from 8.5 to 14.35 Ω−1 cm2 mol−1. IR spectra suggested which the ligand coordinates through the metal ions in a tridentate fashion, utilizing the (N &amp; O) donor sites from the (CN &amp; CO &amp; CO) groups in the hydroxybenzylidene moiety. Analytical data from solution complexation, job's method suggested a 1:1 (metal:ligand) molar ratio. The stability order of the complexes was determined as ITBCo &gt; ITBCu &gt; ITBNi &gt; ITBZn &gt; ITBCd, consistent with the stability constant (Kf) values. The pH profile indicated that the studied complexes exhibit stability upon a wide pH scale, typically between (pH = 4:10). Magnetic and electronic spectral analyses helped deduce the ligand coordination abilities and the geometric structures of the complexes. In vitro (antimicrobial &amp; anticancer) performances of the studied complexes were tested versus various (microbial strains &amp; cancer cell lines), revealing higher activity in the chelates assessed to the free (ITB) ligand. The antioxidant potential was also assessed using the DPPH assay. Finally, molecular docking was performed toward estimate the binding efficiency between various protein receptors and the compounds, with results aligning with the biological investigations.

Atomic-Level Structure of the Organic-Inorganic Interface of Colloidal ZnO Nanoplatelets from Dynamic Nuclear Polarization-Enhanced NMR.

Colloidal semiconductor nanoplatelets (NPLs) have emerged as a new class of nanomaterials that can exhibit substantially distinct optical properties compared to those of isotropic quantum dots, which makes them prime candidates for new-generation optoelectronic devices. Insights into the structure and anisotropic growth of NPLs can offer a blueprint for their controlled fabrication. Here, we present an atomic-level investigation of the organic-inorganic interface structure in ultrathin and stable benzamidine (bza)-supported ZnO NPLs prepared by the modified one-pot self-supporting organometallic approach. High-resolution transmission electron microscopy analysis showed a well-faceted hexagonal shape of ZnO NPLs with lateral surfaces terminated by nonpolar (101̅0) facets. The basal surfaces are flat and well-formed on one side and corrugated on the other side, which indicates that the layer-by-layer growth in the thickness of the NPLs likely occurs only in one direction via the expansion of 2D islands on the surface. The ligand coordination modes were elucidated using state-of-the-art dynamic nuclear polarization (DNP)-enhanced solid-state NMR spectroscopy supported by density functional theory chemical shift calculations. Specifically, it was found that (101̅0) nonpolar facets are stabilized by neutral L-type bza-H ligands with hydrogen bond-supported η1-coordination mode, while polar (0001) and (0001̅) facets are covered by μ2-coordinated X-type anionic bza ligands with different conformations of aromatic rings. Moreover, the ligand packing on (101̅0) lateral facets was determined using 13C natural abundance (∼1.1%) homonuclear dipolar correlation experiments. Overall, an in-depth understanding of the growth mechanism and the unique bimodal X-type/L-type ligand coordination shell of ZnO NPLs is provided, which will facilitate further design of anisotropic nano-objects.

Synthesis of Silver(I) Complexes through In Situ Reactions of dppeda with dmp in the Presence of Silver Halides for Photocatalysis.

Due to the unique photosensitivity of silver compounds, they exhibit good photocatalytic activity as photocatalysts in the degradation of water pollutants. However, silver compounds have poor cycling stability and are prone to decomposition and reaction under light to form metallic silver, which greatly limits their practical application. Herein, a (2-(2-(diphenylphosphaneyl)ethyl)-9-methyl-1.10-phenanthroline (PSNNP)) pincer ligand was designed for stabilizing the central metal. The in situ-formed PSNNP ligand could be readily generated in one pot with the participation of silver halides. The reaction of silver halides with dppeda (N,N,N',N'-tetra(diphenylphosphanylmethyl)ethylene diamine) in the presence of dmp (2,9-dimethyl-1,10-phenanthroline) in acetonitrile afforded complexes Ag2X2 (PSNNP)2 (complexes 1, 2) (X = Cl, Br). Single-crystal X-ray diffraction shows that the tridentate coordination of the pincer ligand provides strong binding with metal centers and leads to high stability of the pincer metal unit. The removal rate of rhodamine B (RhB) by complexes 1 and 2 can reach up to 100%, demonstrating an excellent photocatalytic degradation performance for organic dyes. The important effect of PSNNP ligands on photocatalytic properties after coordination with central metals was studied through experiments and discrete Fourier transform (DFT) calculations. The photocatalytic reaction mechanism of complexes 1 and 2 was also studied. This result provides an effective pathway for the first synthesis of PSNNP and interesting insights into photocatalytic degradation chemistry.

Aggregation-disaggregation regulated fluorescence resonance energy transfer of perovskite nanocrystals for the detection of ascorbic acid

Fluorescence resonance energy transfer (FRET) from fluorescent nanoparticles to small molecules is an attractive approach for bioanalysis. It remains challenging to reversibly regulate the FRET, let alone use reversible FRET to detect ions or molecules. Here we demonstrate an aggregation/disaggregation strategy for reversible regulation of FRET based on metal–ligand coordination chemistry and redox reactions. An amino-functionalized red fluorescent (∼668 nm) perovskite nanocrystals (PNCs) was prepared as the energy donor. Fe3+ can coordinate with the amino groups on PNCs, resulting in the aggregation of PNCs and enhanced absorption from 600 to 700 nm on the surface of PNCs. Aggregation can reduce the distance between PNCs and Fe3+–amino complexes, as well as restrict rotational and translational diffusion of PNCs or Fe3+–amino complexes, consequently enhancing the FRET between PNCs and Fe3+–amino complexes. Interestingly, reductive ascorbic acid can reduce Fe3+ to Fe2+ in the complexes, leading to a weakening of absorption at 668 nm and dispersion of PNCs, resulting in the disappearance of the FRET process involved in PNCs. Based on the FRET switch, we have realized consecutive quantitative analysis of Fe3+ and ascorbic acid in real samples. We expect that reversible FRET process can be regulated by aggregation-disaggregation instructed by coordination and redox reactions, and that the regulation strategy could significantly expand the application scope of PNCs in fluorescence detection.

Ligand‐Directed Synthesis of a Self‐Organized Chloro‐Bridged Cubic Pd(II) Cage Showing Selective Encapsulation of Phenols

AbstractThe synthesis and guest recognition properties of a neutral Pd24‐cubic cage, [{Pd3(NiPr)3PO}8(μ2‐Cl)24] 1 are reported. The formation of the cubical assembly takes place by an exclusive one‐pot ligand‐assisted pathway directed by an oximido linker. The initial coordination of the oximido ligand pre‐organizes the [Pd3(NiPr)3PO]3+ polyhedral building units into a tetrameric intermediate, which then transforms into an oximido‐tethered tetrahedral assembly and to the cubical cage 1 in the presence of chloride ions. In the absence of the directing oximido linker, no cage formation was observed, and the Pd6‐precursor was found to undergo self‐condensation, giving rise to a new pentameric polyhedral cluster, [Pd5{(NiPr)3PO}2(OAc)2(OH)2] 2. The central cavity of the cube has been probed for guest encapsulation studies, which shows a high binding with phenolic guest molecules with association constants of the order of 104–105 M−1. The favorable formation of host–guest complexes was attributed to the strong hydrogen bonding interactions between the host and guest functional groups.

Δ-Bis[(S)-2-(4-isopropyl-4,5-di-hydro-oxazol-2-yl)phenolato-κ2 N,O 1](1,10-phenanthroline-κ2 N,N')ruthenium(III) hexa-fluorido-phosphate.

The title compound, [Ru(C12H14NO2)2(C12H8N2)]PF6 crystallizes in the tetra-gonal Sohnke space group P41212. The two bidentate chiral salicyloxazoline ligands and the phenanthroline co-ligand coordinate to the central RuIII atom through N,O and N,N atom pairs to form bite angles of 89.76 (15) and 79.0 (2)°, respectively. The octa-hedral coordination of the bidentate ligands leads to a propeller-like shape, which induces metal-centered chirality onto the complex, with a right-handed (Δ) absolute configuration [the Flack parameter value is -0.003 (14)]. Both the complex cation and the disordered PF6 - counter-anion are located on twofold rotation axes. Apart from Coulombic forces, the crystal cohesion is ensured by non-classical C-H⋯O and C-H⋯F inter-actions.

Ligand-Directed Synthesis of a Self-Organized Chloro-Bridged Cubic Pd(II) Cage Showing Selective Encapsulation of Phenols.

The synthesis and guest recognition properties of a neutral Pd24-cubic cage, [{Pd3(NiPr)3PO}8(μ2-Cl)24] 1 are reported. The formation of the cubical assembly takes place by an exclusive one-pot ligand-assisted pathway directed by an oximido linker. The initial coordination of the oximido ligand pre-organizes the [Pd3(NiPr)3PO]3+ polyhedral building units into a tetrameric intermediate, which then transforms into an oximido-tethered tetrahedral assembly and to the cubical cage 1 in the presence of chloride ions. In the absence of the directing oximido linker, no cage formation was observed, and the Pd6-precursor was found to undergo self-condensation, giving rise to a new pentameric polyhedral cluster, [Pd5{(NiPr)3PO}2(OAc)2(OH)2] 2. The central cavity of the cube has been probed for guest encapsulation studies, which shows a high binding with phenolic guest molecules with association constants of the order of 104-105 M-1. The favorable formation of host-guest complexes was attributed to the strong hydrogen bonding interactions between the host and guest functional groups.

Exploring Antiplasmodial, Antimicrobial, Antioxidant, and Docking Profile: Conjugating Organotin Moiety With Hydrazones for Enhanced Efficacy

ABSTRACTIn the 21st century, pathogenic deformities contribute significantly to global morbidity and mortality. Our research investigates the antimalarial, antimicrobial, and antioxidant activities of newly synthesized hydrazones and their organotin (IV) complexes, derived from 2‐benzoyl‐1H‐indene‐1,3(2H)‐dione and 2‐phenoxypropanehydrazide/2‐(2,4‐dichlorophenoxy)propanehydrazide. Structural confirmation was achieved through multinuclear nuclear magnetic resonance (NMR), UV–Vis, IR, HRMS, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM)‐energy‐dispersive X‐ray analysis (EDAX), revealing tridentate coordination of ligands to the tin metal via imine nitrogen and two enolic oxygens, forming a pentacoordinated geometry. The SEM analysis revealed that hydrazone ligand (1) exhibits a rectangular bar‐like microstructure, whereas its complex (5) shows a rugged surface with distinct territorial patches. Compounds (5) [Bu2SnL1] and (6) [Ph2SnL1] stood out with significant bioactivity, with antimalarial IC50 values ranging from 0.54 ± 0.07 to 0.67 ± 0.06 μM and antioxidant IC50 values from 4.39 ± 0.02 to 4.67 ± 0.01 μM. Additionally, compounds (6) [Ph2SnL1] and (10) [Ph2SnL4] exhibited the highest antimicrobial activity, with MIC values ranging from 0.0045 to 0.0042 μmol/mL, respectively, comparable to standard drugs. Complementing the experimental data, in silico molecular docking studies were performed on the most effective ligand (1) [H2L1] and its phenyl complex (6) [Ph2SnL1] with Plasmodium falciparum lactate dehydrogenase, revealing binding energies of −6.0 and −6.9 kcal/mol, respectively, and corroborating the experimental findings. Further, comprehensive absorption, distribution, metabolism, excretion, and toxicity (ADMET) evaluations were performed on each compound to gauge their suitability as drug candidates and potential for toxicity.