Ligand Coordination Research Articles

Precise fine-tuning of the defect degree in FeNi-TDC nanoarrays via fluorinated acetic acid for rapid urea-assisted hydrogen production in seawater

Precisely regulating the defect degree in metal-organic framework (MOF) crystals and exploring the structure-activity relationship is of great significance for urea-assisted seawater electrolysis to produce green hydrogen. Herein, a series of X-FeNi-TDC nanoarrays with various defects are successfully constructed through the competitive coordination of ligand 2,5-thiophenedicarboxylic acid (H2TDC) and fluorinated acetic acid modulators with different pKa and coordination ability of -COO. The 20D-FeNi-TDC nanosheets containing more unsaturated sites and moderate electron delocalization exhibit multifunctional activity with an overpotential of 194 mV in OER, 116 mV in HER and an applied voltage of 1.326 V in UOR at 10 mA cm-2. In addition, small angle X-ray scattering (SAXS), small angle neutron scattering (SANS), X-ray absorption near-edge structure (XANES) and density functional theory (DFT) calculation further elucidate alterations in pore structure and electronic arrangement of metal sites. This study provides insight into the mechanism by which modulators regulate defects in MOF-based electrocatalyst.

Selectivity Switching by Ligand Coordination Sites─The Key to Promote the CO2/C2H4 Coupling Reaction over the Ru-Based Catalyst

Selectivity Switching by Ligand Coordination Sites─The Key to Promote the CO₂/C₂H₄ Coupling Reaction over the Ru-Based Catalyst

Insights from Ca2+→Sr2+ substitution on the mechanism of O-O bond formation in photosystem II.

In recent years, there has been a steady interest in unraveling the intricate mechanistic details of water oxidation mechanism in photosynthesis. Despite the substantial progress made over several decades, a comprehensive understanding of the precise kinetics underlying O-O bond formation and subsequent evolution remains elusive. However, it is well-established that the oxygen evolving complex (OEC), specifically the CaMn4O5 cluster, plays a crucial role in O-O bond formation, undergoing a series of four oxidative events as it progresses through the S-states of the Kok cycle. To gain further insights into the OEC, researchers have explored the substitution of the Ca2+ cofactor with strontium (Sr), the sole atomic replacement capable of retaining oxygen-evolving activity. Empirical investigations utilizing spectroscopic techniques such as XAS, XRD, EPR, FTIR, and XANES have been conducted to probe the structural consequences of Ca2+→Sr2+ substitution. In parallel, the development of DFT and QM/MM computational models has explored different oxidation and protonation states, as well as variations in ligand coordination at the catalytic center involving amino acid residues. In this review, we critically evaluate and integrate these computational and spectroscopic approaches, focusing on the structural and mechanistic implications of Ca2+→Sr2+ substitution in PS II. We contribute DFT modelling and simulate EXAFS Fourier transforms of Sr-substituted OEC, analyzing promising structures of the S3 state. Through the combination of computational modeling and spectroscopic investigations, valuable insights have been gained, developing a deeper understanding of the photosynthetic process.

Impact of ligand fields on Kubas interaction of open copper sites in MOFs with hydrogen molecules: an electronic structural insight.

We investigate hydrogen sorption on open copper sites in various ligand coordinations of metal-organic frameworks (MOFs), including the triangular T(CuL3) in MFU-4l, the linear L(CuL2) in NU2100, and the paddlewheel P(CuL4)2 in HKUST-1 from an electronic structure perspective using DFT calculations. The ligand-field-induced splitting of d states and spd hybridizations in copper are thoroughly examined. The hybridization between Cu s, p, and d orbitals occurs in various forms to optimize the Coulomb repulsion of different ligand fields. Despite the Cu+ oxidation state, which is typically conducive to strong Kubas interactions with hydrogen molecules, the vacant spd z 2 hybrid orbitals of the open copper site in the L(CuL2) coordination are unsuitable for facilitating electron forward donation, thereby preventing effective hydrogen adsorption. In contrast, the vacant spd z 2 hybrid orbitals in the T(CuL3) and P(CuL4)2 coordinations can engage in electron forward donations, forming bonding states between the Cu spd z 2 and H2 σ bonding orbitals. The forward donation in the T(CuL3) configuration is significantly stronger than in the P(CuL4)2 configuration due to both the lower energy of the vacant orbitals and the larger contributions of p and d z 2 characters to the hybrid orbital. Additionally, the occupied Cu pd xz/yz and pd x 2-y 2 hybrid orbitals in the T(CuL3) configuration promote electron back donation to the H2 σ* antibonding orbital, leading to the formation of π bonding states. In the P(CuL4)2 coordination, the repulsion from the electron density distributed over the surrounding ligands prevents the H2 molecule from approaching the copper center closely enough for the back donation to occur. The complete Kubas interaction, involving both forward and back electron donations, results in a large dihydrogen-copper binding energy of 37.6 kJ mol-1 in the T(CuL3) coordination. In contrast, the binding energy of 10.6 kJ mol-1 in the P(CuL4)2 coordination is primarily driven by electrostatic interactions with a minor contribution of the Kubas-like forward donation interaction. This analysis highlights the pivotal role of coordination environments in determining the hydrogen sorption properties of MOFs.

Research Progress of Metal-Organic Frameworks as Drug Delivery Systems.

Metal-organic frameworks (MOFs) are composite crystalline materials created through the coordination of metal ions and organic ligands. MOFs have attracted extensive attention in the biomedical field based on the advantages of internal porosity, customizable porosity, and facile surface modification. This review examines the utilization of MOFs in drug delivery systems, focusing on the research progress from the aspects of coloading drug systems, intelligent responsive carriers, biological macromolecule stabilizers, self-driving micro/nanomotors, and multifunctional living carriers. In addition, the current challenges the research faces are also discussed. The review aims to provide a reference for the further application of MOFs as advanced drug delivery systems.

A General Descriptor for Single‐Atom Catalysts with Axial Ligands

AbstractDecoration of an axial coordination ligand (ACL) on the active metal site is a highly effective and versatile strategy to tune activity of single‐atom catalysts (SACs). However, the regulation mechanism of ACLs on SACs is still incompletely known. Herein, we investigate diversified combinations of ACL‐SACs, including all 3d–5d transition metals and ten prototype ACLs. We identify that ACLs can weaken the adsorption capability of the metal atom (M) by raising the bonding energy levels of the M−O bond while enhancing dispersity of the d orbital of M. Through examination of various local configurations and intrinsic parameters of ACL‐SACs, a general structure descriptor σ is constructed to quantify the structure–activity relationship of ACL‐SACs which solely based on a few key intrinsic features. Importantly, we also identified the axial ligand descriptor σACL, as a part of σ, which can serve as a potential descriptor to determine the rate‐limiting steps (RLS) of ACL‐SACs in experiment. And we predicted several ACL‐SACs, namely, CrN4‐, FeN4‐, CoN4‐, RuN4‐, RhN4‐, OsN4‐, IrN4‐ and PtN4‐ACLs, that entail markedly higher activities than the benchmark catalysts of Pt and IrO2 for oxygen reduction reaction and oxygen evolution reaction, respectively, thereby supporting that the general descriptor σ can provide a simple and cost‐effective method to assess efficient electrocatalysts.

Understanding and Controlling Reactivity Patterns of Pd1@C3N4-Catalyzed Suzuki-Miyaura Couplings.

Using heterogeneous single-atom catalysts (SACs) in the Suzuki-Miyaura coupling (SMC) has promising economic and environmental benefits over traditionally applied palladium complexes. However, limited mechanistic understanding hinders progress in their design and implementation. Our study provides critical insights into the working principles of Pd1@C3N4, a promising SAC for the SMC. We demonstrate that the base, ligand, and solvent play pivotal roles in facilitating interface formation with reaction media, activating Pd centers, and modulating competing reaction pathways. Controlling the previously overlooked interplay between base strength, reagent solubility, and surface wetting is essential for mitigating mass transfer limitations in the triphasic reaction system and promoting catalyst reusability. Optimum conditions for Pd1@C3N4 require polar solvents, intermediate base strength, and increased water content. Our investigations reveal that high selectivity requires minimizing competitive coordination of bases and phosphine ligands to the Pd centers, to avoid homocoupling and alternative reductive elimination mechanisms giving rise to phosphonium side-products. Furthermore, in situ XAS investigations probing electronic structures and coordination environments of Pd sites further rationalize the base and ligand coordination, confirming and expanding upon previous computational hypotheses for Pd1@C3N4. This understanding allows for designing a more selective ligand-free reaction pathway using the solvent and base to modulate the chemical environment of the active sites. We highlight the importance of environment-compatible surface tension, the creation of coordinatively available active sites, and the stabilization of partially reduced Pd centers, emphasizing the importance of mechanistic studies to advance the design of SACs in organic liquid phase reactions.

Chelation Protection for Zinc Anode of Aqueous Batteries

AbstractThis mini‐review comprehensively outlines the latest advancements in protecting zinc anodes in zinc‐ion batteries (ZIBs) through chelation mechanisms. Chelation involves the coordination of ligands with Zn2+, offering promising strategies to address challenges such as dendrite formation and hydrogen evolution reactions. However, there is a lack of comprehensive and unified evaluation of chelation‘s protective effect on the zinc anode, which hinders a thorough assessment of chelation‘s effectiveness. Recent studies have demonstrated the excellent protective performance of chelation in altering solvation structures, modifying SEI structures, and selectively adsorbing species on the zinc anode. Furthermore, while chelation demonstrates significant benefits for the zinc anode, its impact on cathode materials must also be considered. Proper selection of chelation strengths and compatible cathode materials is essential for overall battery performance. Future research directions include exploring the effects of different ligands and coordination numbers on battery performance and extending chelation strategies to other secondary metal batteries. Understanding and optimizing chelation mechanisms are critical for advancing the development of high‐performance ZIBs and other metal‐ion battery technologies.

Molecular structure regulation and herbicidal activity of dibutyltin aryloxyacetate complexes

Six dibutyltin aryloxyacetate complexes [(X-C6H4OCH2COO)(SnBu2)2(μ3O)(OMe)]2 (A1, B1), [(X-C6H4OCH2COO)2(SnBu2)2(μ3O)]2 (A2, B2), and [(X-C6H4OCH2COO)2SnBu2] (A3, B3) were synthesized and characterized by IR, NMR, HRMS, and TGA techniques. The molecular structure of complexes A1, A3 and B1-B3 was confirmed by single-crystal X-ray crystallography. Complexes A1, B1, A2, and B2 are dimeric carboxylate tetraorganodistannoxanes, displaying a "ladder-like" molecular arrangement. The aryloxyacetate ligands in A1 and B1 adopt a monodentate mode, while they function as bridging coordination ligands in A2 and B2. Complexes A3 and B3 represent dibutyltin carboxylates with crystallographically imposed two-fold symmetry, with the aryloxyacetate ligands adopting a bidentate mode. Aryloxyacetic acids demonstrate a propensity for assuming various coordination modes, leading to the formation of diverse molecular architectures in organotin carboxylates. In addition, complex B1 exhibits polymorphism. Echinochloa crus-galli and Portulaca oleracea L. were used as target organisms for herbicidal activity testing using a petri dish method. It was found that they have a significant inhibitory effect on weed roots and stems at 200 μmol/L, and the structure-activity relationship analysis revealed the important influence of substituent types and complex structures on their activity.

Tuning the Coordination Environment of Ru(II) Complexes with a Tailored Acridine Ligand.

A novel tridentate ligand featuring an acridine core and pyrazole rings, namely 2,7- di-tert-butyl-4,5-di(pyrazol-1-yl)acridine, L, was designed and used to create two ruthenium(II) complexes: [RuL2](PF6)2 and [Ru(tpy)L](PF6)2. Surprisingly, the ligand adopted different coordination modes in the complexes: facial coordination for the homoleptic complex and meridional coordination for the heteroleptic complex. The electronic absorption and electrochemical properties were evaluated. Although both complexes exhibited favorable electronic properties for luminescence, neither emitted light at room temperature nor at 77 K. This study highlights the complex interplay between ligand design, coordination mode, and luminescence in ruthenium(II) complexes.

Dyotropic Rearrangement of an Iron–Aluminium Complex

Ligand exchange processes at metal complexes underpin their reactivity and catalytic applications. While mechanisms of ligand exchange at single site complexes are well established, occurring through textbook associative, dissociative and interchange mechanisms, those involving heterometallic complexes are less well developed. Here we report the reactions of a well‐defined Fe–Al hydride complex with exogeneous ligands (CO and CNR, R = Me, tBu, Xyl = 2,6‐Me2C6H3). Based on DFT calculations we suggest that these reactions occur through a dyotropic rearrangement, this involves initial coordination of the exogenous ligand at Al followed by migration to Fe, with simultaneous migration of a hydride ligand from Fe to Al. Such processes are rare for heterometallic complexes. We study the bonding and mechanism of the dyotropic rearrangement through in‐depth computational analysis (NBO, IBOs, CLMO analysis, QTAIM, NCIplot, IMGH), shedding new light on how the electronic structure of the heterometallic core responds to the migration of ligands between metal sites. The dyotropic rearrangement fundamentally changes the nature of the hydride ligands, exposing new nucleophilic reactivity as evidenced by insertion reactions with CO2, isocyanates, as well as isocyanides.

Dyotropic Rearrangement of an Iron-Aluminium Complex.

Ligand exchange processes at metal complexes underpin their reactivity and catalytic applications. While mechanisms of ligand exchange at single site complexes are well established, occurring through textbook associative, dissociative and interchange mechanisms, those involving heterometallic complexes are less well developed. Here we report the reactions of a well-defined Fe-Al dihydride complex with exogenous ligands (CO and CNR, R=Me, tBu, Xyl=2,6-Me2C6H3). Based on DFT calculations we suggest that these reactions occur through a dyotropic rearrangement, this involves initial coordination of the exogenous ligand at Al followed by migration to Fe, with simultaneous migration of a hydride ligand from Fe to Al. Such processes are rare for heterometallic complexes. We study the bonding and mechanism of the dyotropic rearrangement through in-depth computational analysis (NBO, IBOs, CLMO analysis, QTAIM, NCIplot, IGMH), shedding new light on how the electronic structure of the heterometallic core responds to the migration of ligands between metal sites. The dyotropic rearrangement fundamentally changes the nature of the hydride ligands, exposing new nucleophilic reactivity as evidenced by insertion reactions with CO2, isocyanates, as well as isocyanides.

Recyclable Homogeneous Catalysis Enabled by Dynamic Coordination on Rhodium(II) Axial Sites of Metal-Organic Polyhedra.

The activity of catalytic nanoparticles is strongly dependent on their surface chemistry, which controls colloidal stability and substrate diffusion toward catalytic sites. In this work, we studied how the outer surface chemistry of nanostructured Rh(II)-based metal-organic cages or polyhedra (Rh-MOPs) impacts their performance in homogeneous catalysis. Specifically, through post-synthetic coordination of aliphatic imidazole ligands onto the exohedral Rh(II) axial sites of Rh-MOPs, we solubilized a cuboctahedral Rh-MOP in dichloromethane, thereby enabling its use as a homogeneous catalyst. We demonstrated that the presence of the coordinating ligand on the surface of the Rh-MOP does not hinder its catalytic activity in styrene aziridination and cyclopropanation reactions, thanks to the dynamic Rh-imidazole coordination bond. Finally, we used similar ligand exchange post-synthetic reactions to develop a ligand-mediated approach for precipitating the Rh-MOP catalyst, facilitating the recovery and reuse of Rh-MOPs as homogeneous catalysts.

Unveiling the key role of metal coordination mode and ligand's side groups on the performance of deep-red light-emitting electrochemical cell

Three novel deep-red to near-infrared (DR to NIR) emitters based on mononuclear and dinuclear ruthenium(II) complexes with bulky structures were presented herein. For the first time, the unusual effects of metal coordination mode on the electroluminescence properties of a binuclear emitter were investigated. Unexpectedly, the mononuclear complexes showed superior performance in deep-red light-emitting electrochemical cells (DR-LEC) compared to the dinuclear complex. Likewise, substituting various ancillary ligands improved the radiance and lifetime of devices by 2.5 and 1.5 times, respectively. To the best of our knowledge, the obtained efficiency is among the best reported to date for DR-LECs based on ruthenium polypyridyl complexes.

Computational Design of Bidentate Hypervalent Iodine Catalysts in Halogen Bond-Mediated Organocatalysis.

In recent years, halogen bond-based organocatalysis has garnered significant attention as an alternative to hydrogen-based catalysis, capturing considerable interest within the scientific community. This transition has witnessed the evolution of catalytic scaffolds from monodentate to bidentate architectures, and from monovalent to hypervalent species. In this DFT-based study, we explored a bidentate hypervalent iodine(III)-based system that has already undergone experimental validation. Additionally, we explore various functionalisations (-CF3, -CH3, -tBu, -OH, -OMe, -NO2, -CN) and scaffold modifications, such as sulfur oxidation, theoretically proposed for an indole-based Michael addition. The investigated systems favour bidentate O-type binding, underlining the importance of ligand coordination in catalytic activity. Electron-deficient scaffolds exhibited stronger binding and lower activation energies, indicating the pivotal role of electronic properties for σ-hole-based catalysis. Of these groups, Lewis-base-like moieties formed stabilising intramolecular interactions with hypervalent iodines when in the ortho-position. Furthermore, inductive electron withdrawal was deemed more effective than mesomeric withdrawal in enhancing catalytic efficacy for these systems. Lastly, increasing sulfur oxidation was theoretically proven to improve catalytic activity significantly.

Residues in the fructose-binding pocket are required for ketohexokinase-A activity

Excessive fructose consumption is a primary contributor to the global surges in obesity, cancer, and metabolic syndrome. Fructolysis is not robustly regulated and is initiated by ketohexokinase (KHK). In this study, we determined the crystal structure of KHK-A, one of two human isozymes of KHK, in the apo-state at 1.85 Å resolution, and we investigated the roles of residues in the fructose-binding pocket by mutational analysis. Introducing alanine at D15, N42, or N45 inactivated KHK-A, whereas mutating R141 or K174 reduced activity and thermodynamic stability. Kinetic studies revealed that the R141A and K174A mutations reduced fructose affinity by 2- to 4-fold compared to WT KHK-A, without affecting ATP affinity. Molecular dynamics simulations provided mechanistic insights into the potential roles of the mutated residues in ligand coordination and the maintenance of an open state in one monomer and a closed state in the other. Protein–protein interactome analysis indicated distinct expression patterns and downregulation of partner proteins in different tumor tissues, warranting a re-evaluation of KHK’s role in cancer development and progression. The connections between different cancer genes and the KHK signaling pathway suggest that KHK is a potential target for preventing cancer metastasis. This study enhances our understanding of KHK-A's structure and function and offers valuable insights into potential targets for developing treatments for obesity, cancer, and metabolic syndrome.

Introducing the Bis(mesitoyl)phosphide Ligand into Dinuclear Trivalent Rare Earth Metal Coordination Chemistry.

Anionic ancillary ligands play a critical role in the construction of rare earth (RE) metal complexes due to the large influence on the stability of the molecule and engendering emergent electronic properties that are of interest in a plethora of applications. Supporting ligands comprising oxygen donor atoms are highly pursued in RE chemistry owing to the high oxophilicity innate to these ions. The scarcely employed bis(acyl)phosphide (BAP) ligands feature oxygen coordination sites and contain a phosphide backbone rendering it attractive for RE-coordination chemistry. Here, we integrate bis(mesitoyl)phosphide (mesBAP) as an ancillary ligand into REIII chemistry to generate the first dinuclear trivalent RE complexes containing BAP ligands; [{mesBAP}2RE(THF)(μ-Cl)]2 (RE=Y, (1), Gd (2), and Dy (3); THF=tetrahydrofuran). Each RE center is ligated to two monoanionic mesBAP ligands, one THF molecule and one chloride ion. All three molecules were characterized through single-crystal X-ray diffraction, 31P NMR, IR and UV-Vis spectroscopy. 31P, 1H and 13C NMR on the diamagnetic yttrium congener 1 confirm asymmetric ligand coordination. DFT calculations conducted on 2 provided insight into the electronic structure. The magnetic properties of 2 and 3 were investigated via SQUID magnetometry. The GdIII ions exhibit weak antiferromagnetic coupling, corroborated by DFT results.

Robust free-base and metalated corrole radicals with reduction-induced emission

Preparing free-base porphyrinoid radicals that can function as coordination ligands is a challenging task. Here we report the synthesis of a stable, free-base benzocorrole (BC) radical containing only two inner NH protons via a retro-Diels-Alder conversion. The radical character of BC was fully supported by crystallographic analysis, spectroscopic evidence, and theoretical calculations. This neutral radical ligand allowed easy insertion of Zn(II), Ga(III), and Pd(II) ions to produce radical complexes. All these radicals exhibited luminescence-on responses under weak reducing atmosphere, corresponding to the conversion to their aromatic anions. The red fluorescence was observed for BC and its Zn(II) and Ga(III) complexes, and the near-infrared phosphorescence (> 900 nm) was detected for Pd(II) complex at room temperature. Furthermore, Ga(III) corrole exhibited a variation in fluorescence in response to axial coordination. Our findings provide a promising radical platform for coordination and developing novel functional materials with switchable spin and emission.

Structural Diversity of Sn(II) Phosphine Oxide Complexes with Weakly Coordinating Anions and Comparisons with Related Ge(II) and Pb(II) Species

AbstractA series of tin(II) triflate phosphine oxide complexes has been prepared from the reaction of Sn(OTf)2 (OTf− = [O3SCF3]−) with various ratios of OPPh3, OPMe3 or dppmO2 (dppmO2 = Ph2(O)PCH2P(O)Ph2). The complexes [Sn(OPPh3)n][OTf]2 (n = 2, 3 or 4), [Sn(OPMe3)n][OTf]2 (n = 2 or 3) and [Sn(dppmO2)n][OTf]2 (n = 1 or 2) have been isolated in moderate to good yields. Selected germanium(II) and lead(II) analogues have been made for comparison, namely [Ge(OPPh3)n][OTf]2 (n = 2 or 3) and [Pb(OPR3)4][OTf]2 (R = Me, Ph). The effect of changing the weakly coordinating OTf− anion for the non‐coordinating [BArF]− anion was investigated through anion metathesis, furnishing the complexes [Sn(OPPh3)n][BArF]2 (n = 3 or 4) and [Ge(OPPh3)3][BArF]2. The isolated solids were characterised by 1H, 19F{1H}, 31P{1H} and IR spectroscopy and microanalysis. Crystal structures were obtained for all complexes except [Ge(OPPh3)2][OTf]2 and [Sn(OPPh3)3][BArF]2, allowing comparisons of the structural features of these divalent group 14 complexes down the group and as a function of coordination number, ligand sterics and electronics.

Exploring the role of neutral ligands in modulating the photoluminescence of samarium complexes with 1,1,1,5,5,5-hexafluoro-2,4-pentanedione.

Four eight-coordinated luminescent samarium complexes of type [Sm(hfpd)3L2] and [Sm(hfpd)3L'] [where hfpd = 1,1,1,5,5,5-Hexafluoro-2,4-pentanedione L = tri-octyl-phosphine oxide (TOPO) and L' = 1,10-phenanthroline (phen), neocuproine (neoc) and bathocuproine (bathoc) were synthesized via a stoichiometrically controlled approach. This allows for precise control over the stoichiometry of the complexes, leading to reproducible properties. This investigation focuses on understanding the impact of secondary ligands on the luminescent properties of these complexes. Infrared (IR) spectra provided information about the molecular structures, whereas 1H and 13C nuclear magnetic resonance (NMR) spectra confirmed these structural details along with the coordination of ligands to trivalent Sm ion. The UV-vis spectra revealed the molar absorption coefficient and absorption bands associated with the hfpd ligand and photoluminescence (PL) spectroscopy demonstrated intense orange-red emission (648 nm relative to 4G5/2 → 6H9/2) from the complexes. The Commission Internationale de l'Éclairage (CIE) triangles indicated that the complexes emitted warm orange red light with color coordinates (x, y) ranging from (0.62, 0.36) to (0.40, 0.27). The investigation of the band gap as well as color parameters confirms the utility of these complexes in displays and LEDs.