Coordination Geometry Research Articles

Octahedral Iron in Catalytic Sites of Endonuclease IV from Staphylococcus aureus and Escherichia coli.

During Staphylococcus aureus infections, reactive oxygen species cause DNA damage, including nucleotide base modification. After removal of the defective base, excision repair requires an endonuclease IV (Nfo), which hydrolyzes the phosphodiester bond 5' to the abasic nucleotide. This class of enzymes, typified by the enzyme from Escherichia coli, contains a catalytic site with three metal ions, previously reported to be all Zn2+. The 1.05 Å structure of Nfo from the Gram-positive organism S. aureus (SaNfo) revealed two inner Fe2+ ions and one Zn2+ as confirmed by dispersive anomalous difference maps. SaNfo has a previously undescribed water molecule liganded to Fe1 forming an octahedral coordination geometry and hydrogen bonded to Tyr33, an active site residue conserved in many Gram-positive bacteria, but which is Phe in Gram-negative species that coordinate Zn2+ at the corresponding site. The 1.9 Å structure of E. coli Nfo (EcNfo), purified without added metals, revealed that metal 2 is Fe2+ and not Zn2+. Octahedral coordination for the sites occupied by Fe2+ suggests a stereoselective mechanism for differentiating between Fe2+ and Zn2+ in this enzyme class. Kinetics and an inhibitor competition assay of SaNfo reveal product inhibition (or slow product release), especially at low ionic strength, caused in part by a Lys-rich DNA binding loop present in SaNfo and Gram-positive species but not in EcNfo. Biological significance of the slow product release is discussed. Catalytic activity in vitro is optimal at 300 mM NaCl, which is consistent with the halotolerant phenotype of S. aureus.

Harnessing of Cooperative Cu···H Interactions for Luminescent Low‐Coordinate Copper(I) Complexes towards Stable OLEDs

Although two‐coordinate Cu(I) complexes are highly promising low‐cost emitters for organic light‐emitting diodes (OLEDs), the exposed metal center in the linear coordination geometry makes them suffer from poor stability. Herein, we described a strategy to develop stable carbene‐Cu‐amide complexes through installing intramolecular noncovalent Cu···H interactions. The employment of 13H‐dibenzo[a,i]carbazole (DBC) as the amide ligand leads to short Cu···H distances in addition to the Cu–N coordination bond. The resultant Cu(I) complexes exhibit yellow thermally activated delayed fluorescence with photoluminescence quantum yields of up to 86% and radiative decay rate constants on the order of 106 s−1. Comparing with the analogues without Cu···H interactions, the pincer complexes have significantly improved stability. The vacuum‐deposited OLEDs show high‐performance electroluminescence with maximum external quantum efficiencies up to 29.5% and extremely small roll‐offs of only 3.5% at 10,000 cd m‐2. Remarkably, the operational lifetimes (LT90) were determined to be up to 68 h with an initial luminance of 3000 cd m‐2. This work proves a feasible design of robust low‐coordinate metal complexes by leveraging secondary coordination interactions, which helps to overcome the long‐standing stability problem.

Investigation on the effect of complex formation on prominent high static/dynamic first and second hyperpolarizability of Co(II) complex including 4-chloro-Pyridine-2-Carboxylic acid

Nonlinear optical (NLO) materials with promising first- and second-order hyperpolarizabilities play a crucial role in the fields of electronics and optoelectronics. For the metal-organic coordination complexes, the logical selection of an appropriate ligand and metal ion is vital in designing such materials to enhance their NLO response. In this study, a novel Co(II) complex, including 4-Chloro-pyridine-2-carboxylic acid ligand, was synthesized. The crystal structure and spectroscopic properties were determined by XRD, FT-IR, and UV–Vis spectroscopies. B3LYP and CAM-B3LYP level calculations demonstrated that there is a strong electronic absorption band at 356 nm, originating from the metal-ligand charge transfer (MLCT) transfer in the UV–Vis spectrum. Both XRD and FT-IR data demonstrated that the Co(II) complex has a distorted octahedral coordination geometry. The calculations of static and frequency-dependent α, β, and γat frequencies of ω = 0.0856252 a.u (λ = 532 nm) and w = 0.0428126 au. (λ = 1064 nm) for 4Clpca and Co(II) complex have been also carried out using B3LYP and CAM-B3LYP levels. The dc-Kerr effect γ(-ω; ω,0,0) and SHG γ(-2ω; ω,ω,0) parameters for Co(II) complex calculated as 329.59 × 10−36 and 433.93 × 10−36 esu are found as dramatically higher those for single pca ligand (6.0267 × 10−36 and 163.70 × 10−36 esu). So, a significant increase was detected in the parameters of frequency-dependent α (-w; 0), β(-w; w,0), and γ (-w; w,0,0) with complex formation.

Improving macromolecular structure refinement with metal-coordination restraints.

Metals are essential components for the structure and function of many proteins. However, accurate modelling of their coordination environments remains a challenge due to the complexity and diversity of metal-coordination geometries. To address this, a method is presented for extracting and analysing coordination information, including bond lengths and angles, from the Crystallography Open Database. By using these data, comprehensive descriptions of metal-containing components are generated. A stereochemical information generator for a particular component within a specific macromolecule leverages an example PDB/mmCIF file containing the component to account for the actual surrounding environment. A matching process has been developed and implemented to align the derived metal structures with idealized coordinates from a coordination geometry library. Additionally, various strategies, depending on the quality of the matches, were employed to compile distance and angle statistics for the refinement of macromolecular structures. The developed methods were implemented in a new program, MetalCoord, that classifies and utilizes the metal-coordination geometry. The effectiveness of the developed algorithms was tested using metal-containing components from the PDB. As a result, metal-containing components from the CCP4 monomer library have been updated. The updated monomer dictionaries, in concert with the derived restraints, can be used in most structural biology computations, including macromolecular crystallography, single-particle cryo-EM and even molecular mechanics.

Fabrication of Co(II)-based coordination polymer for photocatalytic degradation: Selective removal of cationic methyl violet dye

In this study, a new coordination polymer (CP) was designed and synthesized to evaluate the photocatalytic properties for water remediation. The Co(II)-based CP {[Co(HL)(bid)(H2O)]·2H2O}n (1) was hydrothermally synthesized using the ligand 5-(4′-carboxyphenoxy)isophthalic acid (H3L) and 1,4-bis(1-imidazolyl)-2,5-dimethylbenzene (bid). The coordination polymer (1) has been characterized by various spectral techniques, thermogravimetric (TGA), and single crystal X-ray technique. X-ray data revealed that (1) exhibits 2D framework having an octahedral coordination geometry around the Co(II) ions, having μ1:η1-η1 mode with chromophore CoO4N. FT-IR analysis confirmed the asymmetric monodentate binding modes of the carboxylate ligand. The CP 1 has demonstrated optical semiconducting properties, rendering them promising candidates for photocatalytic applications. The catalyst (1) has been effectively utilized in the breakdown of several organic dyes, such as methylene blue (MB), methyl orange (MO), methyl violet (MV), and rhodamine B (RhB). The results showed that at pH 4, with a dosage of 30 mg of catalyst (1), 92.08 % of MV was degraded at a concentration of 20 ppm. Additionally, the mechanistic pathway for light-driven MV decomposition was investigated through experimental approaches, specifically radical trapping experiments.

Redox Noninnocent Copper(I) Complex Where Metal Is a Spectator and Ligand Is an Actor in the Glaser Coupling Reaction of Alkynes.

An extended trisazo dipyridyl ligand, L, and its copper(I) complex, [1]+, were synthesized and fully characterized. Complex [1]+ has five coordination geometry satisfied by ligand L. L has a low-lying π* orbital; thus, [1]+ showed very facile multiple ligand-based redox events. Moreover, due to the strong π-acceptor nature of L, the Cu(II)/Cu(I) redox potential of [1]+ was anodic (0.62 V). The redox events of both L and [1]+ were characterized using various spectroscopic studies and density functional theory (DFT) calculations. Taking advantage of the multiple facile ligand-based reductions in [1]+, the Glaser coupling reaction of terminal alkynes was explored. Various kinds of alkynes were found to be effective when using [1]+ as a precatalyst. The mechanism of the reaction was investigated thoroughly by several controlled experiments, isolation, and characterization of the intermediates using various spectroscopic studies as well as by single-crystal X-ray structure determination. These studies showed that the L in [1]+ acted not only in the electron transfer events but also as a locus for binding the substrate, breaking and forming bonds, and, finally, releasing the product. Thus, here, the metal mainly acted as a spectator and ligand L acted as an actor.

Ligand Many-Body Expansion as a General Approach for Accelerating Transition Metal Complex Discovery.

Methods that accelerate the evaluation of molecular properties are essential for chemical discovery. While some degree of ligand additivity has been established for transition metal complexes, it is underutilized in asymmetric complexes, such as the square pyramidal coordination geometries highly relevant to catalysis. To develop predictive methods beyond simple additivity, we apply a many-body expansion to octahedral and square pyramidal complexes and introduce a correction based on adjacent ligands (i.e., the cis interaction model). We first test the cis interaction model on adiabatic spin-splitting energies of octahedral Fe(II) complexes, predicting DFT-calculated values of unseen binary complexes to within an average error of 1.4 kcal/mol. Uncertainty analysis reveals the optimal basis, comprising the homoleptic and mer symmetric complexes. We next show that the cis model (i.e., the cis interaction model solved for the optimal basis) infers both DFT- and CCSD(T)-calculated model catalytic reaction energies to within 1 kcal/mol on average. The cis model predicts low-symmetry complexes with reaction energies outside the range of binary complex reaction energies. We observe that trans interactions are unnecessary for most monodentate systems but can be important for some combinations of ligands, such as complexes containing a mixture of bidentate and monodentate ligands. Finally, we demonstrate that the cis model may be combined with Δ-learning to predict CCSD(T) reaction energies from exhaustively calculated DFT reaction energies and the same fraction of CCSD(T) reaction energies needed for the cis model, achieving around 30% of the error from using the CCSD(T) reaction energies in the cis model alone.

Circularly Polarized Phosphorescence Properties of Binuclear Cyclometalated Platinum(II) Complexes Bearing Axially Chiral Schiff-Base Ligands.

The synthesis, structure, and circularly polarized phosphorescence (CPP) properties of axially chiral cyclometalated binuclear platinum(II) complexes were described. A series of optically pure binuclear platinum(II) complexes were synthesized in five steps from commercially available (R)- or (S)-1,1'-bi-2-naphthol (BINOL) as starting materials. Their three-dimensional molecular structures and square-planar coordination geometries were elucidated from X-ray diffraction and 2D NMR analysis. The complexes were found to exhibit red- to near-infrared photoluminescence in solution and in the solid state. Furthermore, dilute DMSO solutions of the enantiopure samples showed red CPP with relatively high luminescence dissymmetry factor (glum) values. Density functional theory (DFT) calculations were conducted to examine their three-dimensional molecular conformations and photophysical properties.

Metal‐Ion‐Coordinated Microenvironments in Covalent Organic Frameworks for Enhanced Photocatalytic CO2 Reduction

AbstractMetal‐coordinated covalent organic frameworks (M‐COFs) have garnered significant attention for their potential in carbon dioxide (CO2) photoreduction. However, the efficient conversion of CO2 to (carbon monoxide) CO remains challenging because of the strong exciton effects from the Coulombic interactions of electron‐hole pairs within the metal‐associated coordination environment. Herein, three benzoxazole (BBO)‐based COF photocatalysts coordinated with cobalt (Co) ions featuring distinct coordination geometries: Co‒N‒O2, Co‒N‒O3, and Co‒N2‒O2 are strategically designed. The exciton dissociation is precisely modulated and the photocatalytic reduction of CO2 is enhanced. Among them, BBO‐COFBPY‐Co demonstrates a significant increase in CO production rate from 5, 024.87 to 10, 552.15 µmol g−1 h−1, and an improvement in the selectivity from 80% to 91%, coupled with excellent stability. Spectral characterizations and density functional theory (DFT) theoretical calculations elucidate that the judicious tuning of the Co atom coordination environment optimized the local electronic structure of the BBO‐COFs which significantly boosts the exciton dissociation, facilitates charge carrier migration within the framework, mitigates the recombination of photogenerated electron‐hole pairs, and reduce the energy barrier of the rate‐determining step. This study provides insight into the pivotal role of metal coordination microenvironments in enhancing the photocatalytic CO2 reduction process and paving the way for new strategies in exciton regulation within COFs.

Coordination geometry flexibility driving supramolecular isomerism of Cu/Mo pillared-layer hybrid networks.

Hydrothermal synthesis led to four novel 3D pillared-layer metal-organic frameworks: [Cu4(4,4'-bipy)4(MoO4)4·0.3H2O]n (1), [Cu(4,4'-bipy)0.5(MoO4)·0.25H2O]n (2), [Cu(4,4'-bipy)(MoO4)·0.1H2O]n (3), and [{Cu(4,4'-bipy)}2(Mo8O26)0.5]n (4). These compounds exhibit diverse supramolecular isomerism within their 3D coordination networks, each incorporating bimetallic {CuMoO} layers linked by 4,4'-bipyridine, demonstrating a remarkable structural diversity. Compound 1 features a 3D network derived from conformational supramolecular isomerism. Its bimetallic layer comprises fused 16-membered {Cu4Mo4O8} and eight-membered {Cu2Mo2O4} rings, with varying O-Cu-O bond angles affecting the network puckering and Cu-Cu distances. In contrast, the coordination networks observed in 2, 3, and 4 correspond to structural supramolecular isomers from the earlier stated networks. In 2, centrosymmetric Cu2+ dimers with distorted square-pyramidal geometry are linked along the c axis by 4,4'-bipyridine, forming 1D {Cu2(4,4'-bipy)}n chains with a Cu-Cu distance of 2.95 Å. Its oxide substructure comprises bilayers of fused 12-membered {Cu3Mo3O6} rings. Crystal structures 3 and 4 are particularly notable for their construction at the Cu+ centers. In compound 4, this isomerism is further influenced by the interplay between the distortion of the coordination geometry of both the Cu and Mo ions. The propensity to form these supramolecular isomers primarily stems from the flexible coordination environment of copper ions. Electron paramagnetic resonance measurements corroborated the structural descriptions of the paramagnetic compounds 1 and 2.

Structural, catalytic, antimicrobial and antioxidant properties of Cu(II)-complexes prepared by o-hydroxy Schiff bases with fluorine and ethoxy substituents

Cu(II) complexes of three Schiff bases were synthesized and characterized via X-ray diffraction, Fourier transform infrared, and UV–vis spectroscopies. The Schiff bases act as bidentate ligands, chelating Cu(II) ions in seesaw coordination geometry. Changing the substituent types and positions creates various non-covalent interactions within the crystal packings, yielding notable topological differences. GC–MS analysis reveals that Cu(II) complexes induce 1.38%–11.43% efficacy in Suzuki–Miyaura cross-coupling reactions. The biological activity of complexes correlates with substituent type and position in the aromatic ring. The one with ethoxy exhibits antimicrobial effects solely against Candida parapsilosis, while those with fluorine enhance the activity, particularly in the meta position.

Synchrotron-Based Characterizations of Electrocatalytic Metal-Organic Frameworks and Covalent Organic Framework-Based Solid Electrolyte Interphase for Stabilizing Anode of Rechargeable Batteries

Considering energy-related technologies including rechargeable batteries and water electrolysis, effective catalytic materials play a crucial role in the rise and unceasing development. Metal-organic frameworks (MOFs) have drawn attention due to their abundant and identical catalytic sites along the periodic network with tunable catalytic functionality and stability. Herein, structural information, catalytic sites, and their corresponding mechanistic pathways have been investigated by employing synchrotron-based X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). The framework stability, the accessible active sites related to pre-designed metal clusters, the alteration of oxidation state of, and the coordination geometry around the active metal centers evolving along the electrochemical oxygen evolution reaction (OER) are thoroughly revealed. In addition, aqueous zinc-ion batteries (AZIBs) are promising energy storage systems due to their cost-effectiveness and eco-friendliness. However, there are some limitations restricting their practical utilizations such as the high activity of water leading to Zn corrosion and hydrogen evolution, along with the formation of dendrites on the Zn surface during repeated charge–discharge cycles. To limit parasitic side reactions, an artificial solid electrolyte interphase (ASEI) protective layer made of a covalent organic framework (COFs) is an effective strategy. Herein, grazing-incidence XAS was employed to specifically characterize the Zn speciation on the electrode surface. According to XAS results, the protective COF-ASEI layer can retard the coordination of water at the electrolyte–Zn interface, improve Zn plating/stripping kinetics, and increase the stability of the Zn anode. This presentation highlights the significance of synchrotron characterizations in energy-related technologies.

Self‐Organization of Relaxed Structures in the Lunar Atmosphere

ABSTRACTThe study investigates the relaxation of a three‐component dusty plasma in the lunar atmosphere. By employing Ampère's law with momentum balance equation of the plasma species, which includes an electron, a positive ion, and a negatively charged dust particle, a Triple Beltrami (TB) state is obtained. This TB state is characterized by three scale parameters, which may be real or complex. The Cartesian coordinate geometry is employed to analyze the magnetic field profiles. The Beltrami parameters, mass of negative charged dust particulates and density variations at different height and angle have a significant impact on the magnetic properties of the self‐organized structures in lunar atmosphere. The study reveals that all scale parameters associated with diamagnetic structures are real and complex, while all scale parameters for paramagnetic structures are real. It has been shown that the magnetic field, along with its complex conjugate and real part, increases with height and angle, and only diamagnetic structures are formed in the lunar atmosphere. The findings of this study should help to explain relaxed structures found in other astronomical objects and in lab settings including negatively charged dust particles, ions, and electrons.

Ligand-Directed Valence Band Engineering in Pb2+ Hybrid Crystals: Achieving Dispersive Bands and Shallow Valence Band Maximum.

While crystalline hybrid solids hold great potential as novel semiconductors, most semiconductive hybrids utilize transition metal ions, which inherently limit carrier mobility due to the small band dispersion derived from the d orbitals. The filled s orbitals of post-transition metal ions offer the potential to design dispersed valence bands, but a method to translate the local structure design of these metal ions to valence band engineering is still in development. This study focuses on Pb2+-containing hybrid crystals, developing a simple strategy to control the Pb2+ coordination geometry through the molecular design of azole ligands. By preprogramming the coordination number of Pb2+ with azolate ligands, we succeeded in obtaining an isotropic coordination environment at a higher coordination number, resulting in a dispersed valence band and shallow valence band maximum while having a wide band gap. Detailed analysis of the band structures reveals that the energy levels and symmetry of the molecular orbitals of the anions play important roles in realizing these antinomic properties. This ligand-directed approach achieves both isotropy and covalency in the coordination bond by exploiting the diversity of the molecular orbitals. Our findings provide a foundation for future design strategies to optimize electronic structures in hybrid materials, advancing their application in semiconductive devices.

The Impact of Coordination Distortion on Magnetic Properties of Co (II) Single‐Ion Magnets With Trigonal Prism Coordination Geometry

ABSTRACTTwo Co (II) compounds [Co (abs)2]·2H2O (1) and [Co (pabs)2] (2) (Habs = N‐(pyridine‐2′‐yl methylene)‐2‐aminobenzene sulfonic acid, Hpabs = N‐[(pyridine‐2′‐yl)(phenyl)methylene]‐2‐aminobenzene sulfonic acid) were synthesized by the introduction of sulfonate ligands with different substitutions. Both Co (II) ions are located in a trigonal prism coordination environment with different coordination distortions. Static magnetic studies and theoretical calculations found that easy‐axis magnetic anisotropy is present in both complexes. The contributions of the negative D values are principally derived from the first quartet excited state. Dynamic magnetic investigations uncovered that both compounds have field‐induced single‐ion magnet (SIM) behavior and their magnetic relaxations mainly realize through Raman and direct pathways.

Linear Inverse Sandwich Complexes of Tetraanionic Benzene Stabilized by Covalent δ-Bonding with Late Lanthanides.

A series of dilanthanide benzene inverse sandwich complexes of the type (CpiPr5Ln)2(μ-η6:η6-C6H6) (1-Ln) (Ln = Y, Gd, Tb, Dy, Tm) are reported. These compounds are synthesized by reduction of the respective trivalent dimers CpiPr52Ln2I4 (Ln = Y, Gd, Tb, Dy, Tm) in diethyl ether with potassium graphite in the presence of benzene, and they feature an unusual linear coordination geometry with a highly planar benzene bridge as verified by single-crystal X-ray diffraction. The Ln-Bzcentroid distances of 1-Ln are the shortest distances observed to date, ranging from 1.943(1) Å for 1-Tm to 2.039(6) Å for 1-Gd. Structural, spectroscopic, and magnetic analyses together with density functional theory calculations support the presence of a rare, unsubstituted tetraanionic benzene in each compound, which is stabilized by strong covalent δ bonding interactions involving the filled π* orbitals of (C6H6)4- and vacant dxy and dx2-y2 orbitals of the Ln3+ ions. Notably, 1-Ln are the first examples of compounds of the later lanthanides to feature an unsubstituted tetraanionic benzene.

Intermolecular Interactions in Molecular Ferroelectric Zinc Complexes of Cinchonine

The use of chiral organic ligands as linkers and metal ion nodes with specific coordination geometry is an effective strategy for creating homochiral structures with potential ferroelectric properties. Natural Cinchona alkaloids, e.g., quinine and cinchonine, as compounds with a polar quinuclidine fragment and aromatic quinoline ring, are suitable candidates for the construction of molecular ferroelectrics. In this work, the compounds [CnZnCl3]·MeOH and [CnZnBr3]·MeOH, which crystallize in the ferroelectric polar space group P21, were prepared by reacting the cinchoninium cation (Cn) with zinc(II) chloride or zinc(II) bromide. The structure of [CnZnBr3]·MeOH was determined from single-crystal X-ray diffraction analysis and was isostructural with the previously reported chloride analog [CnZnCl3]·MeOH. The compounds were characterized by infrared spectroscopy, and their thermal stability was determined by thermogravimetric analysis and temperature-modulated powder X-ray diffraction experiments. The intermolecular interactions of the different cinchoninium halogenometalate complexes were evaluated and compared.

High-precision non-contact online measurement and predictive analysis of geometric parameters in large industrial components

Obtaining precise geometric parameters is fundamental in industry but often proves challenging, particularly for large-scale and irregularly shaped industrial components. This study introduces an innovative measurement method enabling precise determination of chord length, arc length, and curvature radius in curved sections of such components, even within dynamic industrial environments. Our solution relies on the implementation of a LiDAR sensor and the utilization of data processing techniques, including outlier detection and removal, as well as customized digital filters. Additionally, we incorporate analytic geometry to address specific measurement challenges. Finally, Machine Learning techniques were applied to forecast time series data of the measurements. The proposed system was validated in a real-world wind turbine tower manufacturing environment, comparing them with manual measurements performed by experienced operators. This validation confirms its effectiveness of our approach, achieving the industry-required minimum tolerances of 5 millimeters, where precise geometric data acquisition is crucial to ensure product quality.

Improving the Lithography Sensitivity of Atomically Precise Tin-Oxo Nanoclusters via Heterometal Strategy.

Tin-oxo clusters are increasingly recognized as promising materials for nanolithography technology due to their unique properties, yet their structural impacts on lithography performance remain underexplored. This work explores the structural impacts of heterometal strategies on the performance of tin-oxo clusters in nanolithography, focusing on various metal dopants and their coordination geometries. Specifically, SnOC-1(In), SnOC-1(Al), SnOC-1(Fe), and SnOC-2 were synthesized and characterized. These clusters demonstrate excellent solubility, dispersibility, and stability, facilitating the preparation of high-quality films via spin-coating for lithographic applications. Notably, this work innovatively employs Atomic Force Microscopy-based Infrared Spectroscopy (AFM-IR), neutron reflectivity (NR), and X-ray reflectivity (XRR) measurements to confirm film homogeneity. Upon electron beam lithography (EBL), all four materials achieve 50 nm line patterns, with SnOC-1(In) demonstrating the highest lithography sensitivity. This enhanced sensitivity is attributed to indium dopants, which possess superior EUV absorption capabilities and unsaturated coordination environments. Further studies on exposure mechanisms indicated that Sn-C bond cleavage generates butyl free radicals, promoting network formations that induce solubility-switching behaviors for lithography. These findings underscore the efficacy of tailored structural design and modulation of cluster materials through heterometal strategies in enhancing lithography performance, offering valuable insights for future material design and applications.

Improving the Lithography Sensitivity of Atomically Precise Tin‐Oxo Nanoclusters via Heterometal Strategy

AbstractTin‐oxo clusters are increasingly recognized as promising materials for nanolithography technology due to their unique properties, yet their structural impacts on lithography performance remain underexplored. This work explores the structural impacts of heterometal strategies on the performance of tin‐oxo clusters in nanolithography, focusing on various metal dopants and their coordination geometries. Specifically, SnOC‐1(In), SnOC‐1(Al), SnOC‐1(Fe), and SnOC‐2 were synthesized and characterized. These clusters demonstrate excellent solubility, dispersibility, and stability, facilitating the preparation of high‐quality films via spin‐coating for lithographic applications. Notably, this work innovatively employs Atomic Force Microscopy‐based Infrared Spectroscopy (AFM‐IR), neutron reflectivity (NR), and X‐ray reflectivity (XRR) measurements to confirm film homogeneity. Upon electron beam lithography (EBL), all four materials achieve 50 nm line patterns, with SnOC‐1(In) demonstrating the highest lithography sensitivity. This enhanced sensitivity is attributed to indium dopants, which possess superior EUV absorption capabilities and unsaturated coordination environments. Further studies on exposure mechanisms indicated that Sn−C bond cleavage generates butyl free radicals, promoting network formations that induce solubility‐switching behaviors for lithography. These findings underscore the efficacy of tailored structural design and modulation of cluster materials through heterometal strategies in enhancing lithography performance, offering valuable insights for future material design and applications.