Molecular Structure Research Articles

Synthesis and properties of silicone-modified polyurethane acrylate for magnetically driven blue light photocurable superhydrophobic coatings

A low surface energy silicone-modified polyurethane acrylate (Si-PUA) has been synthesized and employed as the primary constituent for the magnetically driven photocurable coatings. By integrating magnetically driven assembly technology with blue light photocuring technology, a superhydrophobic coating featuring low surface energy and micro/nano rough structures was successfully fabricated. The influences of hydroxy-terminated polydimethylsiloxane (PDMS) content and the R-value (-NCO/-OH) on the performance of PUA and coating systems were investigated using Photo-DSC, TGA, rheology, tensile testing machine, and SEM-EDS. The molecular structure of Si-PUA was characterized using FT-IR and 1HNMR. The result revealed that the composite coating exhibited a minimum surface energy when the PDMS content was 5 wt% and the R-value was 1.6, resulting in a surface free energy of 24 mJ/m2. When the coating formulation consists of a Si-PUA:HEA ratio of 7:3, an initiator dosage of 2% (with CQ/EDB at a 1:1 ratio), and a carbonyl iron powder (CIP) content of 100 wt%, the resulting photocured film exhibits a surface contact angle of 157.6° and a rolling angle of 5°, thereby satisfying the superhydrophobicity standard.

Organocatalytic Approaches towards the Synthesis of Asymmetric Tetrahydroquinoline (THQ) Derivatives

Among the N-heterocyclic compounds, the delightful 1,2,3,4-tetrahydroquinolines (THQs) shine brightly due to their abundant presence in molecules of significant biological importance and pharmaceuticals with diverse biological activities. Charming derivatives like angustureine and cuspareine spring from the Galipea officinalis, while the captivating martinelline and martinellic acid are treasures from Martinella iquitosenses. The allure of THQs lies in their vast biological potential and the intriguing challenge of natural isolation. To capture these gems, various synthetic routes have been crafted, such as the hydrogenation of quinolines, domino reactions, intramolecular cyclization, and notably, the ingenious Povarov reaction. As the 21st century dawned, a new star ascended in the realm of asymmetric synthesis: organocatalysis. celebrated as the "third pillar" alongside metal catalysts and biocatalysts, organocatalysis employs small, chiral organic molecules to gracefully orchestrate organic transformations under gentle conditions. This approach not only offers remarkable efficiency but also crafts complex molecular structures with high precision. Its simplicity and the accessibility of catalytic systems have made organocatalysis a beloved method, ensuring high yields and exceptional enantiomeric excess across a myriad of organic reactions.

Recent advances in liquid-phase NMR of the coal-derived products.

Present review focuses on the most recent advances in a liquid-phase nuclear magnetic resonance (NMR) of the coal-derived products-coal tar pitches, asphaltenes, and humic and fulvic acids, covering exclusively the results in the liquid-phase NMR studies leaving apart an overwhelming amount of publications dealing with the solid-state NMR investigations in this field (which are comprehensively reviewed elsewhere). Owing to the complexity of the coal-derived products, their 1H and 13C NMR spectra consist of a number of overlapping signals belonging to different hydrocarbon types. Comprehensive studies of coal tar pitches, asphaltenes, and humic and fulvic acids by means of NMR over the past several decades revealed characteristic functional groups of those fractions together with spectral regions in which they resonate. Quantitative 1H and 13C NMR spectra characterize aromatic and saturated carbons spread over many structural moieties, which provides a solid guideline into molecular structure of the coal-derived products. Nowadays, quantitative 13C NMR measurements yield information about a variety of structural parameters such as functional group distribution, aromaticity, degree of condensation of aromatic rings, and medium chain lengths together with many other more specific parameters. The structural NMR studies of coal and coal-derived products are developing on a backdrop of a marked progress in computational NMR. At present, we are witnessing an unprecedentedly fast development of theoretical and computational methods in the field of NMR spectroscopy. Discussed in the present review are the most recent advances in the NMR studies of the processing products of peat, lignite or brown coal, anthracite or hard coal, and graphite in solution, like coal tar pitches, asphaltenes, and humic and fulvic acids.

The Phase Equilibria of Natural Gas Hydrate in the Presence of 1,3-Dimethylcyclohexane and Octyl-β-D-glucopyranoside

The thermodynamic effect of octyl-β-D-glucopyranoside (OGP) on the formation of methane-1,3-dimethylcyclohexane (DMCH) hydrate was studied in this work. The thermodynamic equilibrium hydrate formation pressures between 275.15 K and 283.15 K were measured by the isothermal pressure search method. Different OGP aqueous solutions (0, 0.1, and 1 wt%) were used in this work. The experimental results show that OGP had no obvious thermodynamic inhibition on methane-DMCH hydrate formation when its concentration was low (0.1 wt%), whereas it had an inhibition on methane-DMCH hydrate formation when its concentration was high (1 wt%). The phase equilibrium hydrate formation pressure of the methane-DMCH-OGP system is about 0.1 MPa higher than that of the methane-DMCH system. The dissociation enthalpies of methane hydrate in different solutions remained uniform, which indicates that OGP was not involved in methane-DMCH hydrate formation. This phenomenon is explained from the perspective of the molecular structure of OGP. As a renewable and biological nonionic surfactant, the concentration of OGP in the liquid phase is low, so OGP can be added to the methane-DMCH system without significant thermodynamic inhibition.

One-Stage Pathway from Hollongdione to C17-Alkyne and Vinyl Chloride Following Mannich Bases and Carboxylic Acid

Hollongdione is the first recorded example of the occurrence of a dammarane hexanor-triterpene in nature possessing antiviral and cytotoxic activity. Its simple one-stage transformation into compounds with terminal alkyne and vinyl chloride fragments via the interaction with phosphorus halides is reported. The copper(I)-catalyzed Mannich reaction of 3-oxo-22,23,24,25,26,27-hexanor-dammar-20(21)-in 3 led to a series of aminomethylated products, while 17-carboxylic acid was obtained by ozone oxidation of 3-oxo-22,23,24,25,26,27-hexanor-dammar-20-chloro-20(21)-en 4; the following direct amidation of the latter has been developed. The structures of all new molecules were established by spectroscopic studies that included 2D NMR correlation methods; the molecular structures of compounds 2–5 were determined by X-ray analysis.

Study on the regulation of ε-CL-20 by an external electric field.

To explore the influence of the external electric field (EEF) on ε-CL-20. The molecular structure, frontier molecular orbitals (FMOs), global reactivity parameters (GRP), surface electrostatic potential, nitro charge, and UV-Vis spectra of ε-CL-20 under EEF were studied using density functional theory (DFT). The calculation results show that the electric field applied along N16-N24 has a significant effect on the structure of ε-CL-20. With an increase in the positive EEF, the bond length of the initiating bond decreases, and the bond order and bond dissociation energy increase, which increases the thermal stability of ε-CL-20 to a certain extent. In addition, with an increase in the positive EEF intensity, the LUMO migrates from both sides of the positive electric field to one side of the nitro group, and the HOMO migrates from the skeleton to the nitro group. It is worth noting that in the negative EEF, when the electric field strength changed from 0 to 0.016 a.u., the negative charge of the total nitro group gradually decreased. When the electric field strength becomes 0.02 a.u., the negative charge of the total nitro group suddenly increases, and ε-CL-20 is significantly polarized. When the electric field strength is sufficiently strong, the occupied and unoccupied orbitals of the ε-CL-20 molecule change, resulting in a change in the energy level difference between the occupied and unoccupied orbitals, which further excites the corresponding excited state, resulting in a new UV-Vis absorption peak. Based on the density functional theory (DFT), the structural optimization and energy calculation were carried out by using B3LYP/6-311 + G(d, p) and B3LYP/def2-TZVPP methods, respectively. After optimization convergence, vibration analysis was performed without imaginary frequencies to obtain stable configurations. Then the molecular structure, frontier molecular orbitals (FMOs), global reactivity parameters (GRP), surface electrostatic potential, nitro charge, and UV-Vis spectra were analyzed.

Prediction study of Optical, structural and electronic properties of WClx (x = 3 to 6)

The molecular structures of WCl6, WCl5, WCl4, WCl3 have been optimized by density functional theory calculations. We report the stability of the phases in the ground state, the total energies and the optoelectronic properties of the W-Cl system. We find that the material having a low tungsten concentration shows a low DOS at the Fermi level, which implies a high resistivity. Both polymorphs of WCl6 are crystalline solids at room temperature and show the (α- WCl6) and (β- WCl6) phases of space group R-3 and P-3 m1 observed at 228 °C. The change in temperature influences the structural, electronic and optical properties. The object of this paper does not concern only the study of all phases, but also one controls the physical states of the molecular materials when they are subjected to polymorphic changes. Calculations on the molecular structure under symmetry indicated an orbitally degenerate ground state with bond distances in good agreement with experiment.

Fully Flexible Molecular Alignment Enables Accurate Ligand Structure Modeling.

Accurate protein-ligand binding poses are the prerequisites of structure-based binding affinity prediction and provide the structural basis for in-depth lead optimization in small molecule drug design. However, it is challenging to provide reasonable predictions of binding poses for different molecules due to the complexity and diversity of the chemical space of small molecules. Similarity-based molecular alignment techniques can effectively narrow the search range, as structurally similar molecules are likely to have similar binding modes, with higher similarity usually correlated to higher success rates. However, molecular similarity is not consistently high because molecules often require changes to achieve specific purposes, leading to reduced alignment precision. To address this issue, we propose a new alignment method─Z-align. This method uses topological structural information as a criterion for evaluating similarity, reducing the reliance on molecular fingerprint similarity. Our method has achieved success rates significantly higher than those of other methods at moderate levels of similarity. Additionally, our approach can comprehensively and flexibly optimize bond lengths and angles of molecules, maintaining a high accuracy even when dealing with larger molecules. Consequently, our proposed solution helps in achieving more accurate binding poses in protein-ligand docking problems, facilitating the development of small molecule drugs. Z-align is freely available as a web server at https://cloud.zelixir.com/zalign/home.

Ultrathin Boron Growth onto Nanodiamond Surfaces via Electrophilic Boron Precursors.

Diamond as a templating substrate is largely unexplored, and the unique properties of diamond, including its large bandgap, thermal conductance, and lack of cytotoxicity, makes it versatile in emergent technologies in medicine and quantum sensing. Surface termination of an inert diamond substrate and its chemical reactivity are key in generating new bonds for nucleation and growth of an overlayer material. Oxidized high-pressure high temperature (HPHT) nanodiamonds (NDs) are largely terminated by alcohols that act as nucleophiles to initiate covalent bond formation when an electrophilic reactant is available. In this work, we demonstrate a templated synthesis of ultrathin boron on ND surfaces using trigonal boron compounds. Boron trichloride (BCl3), boron tribromide (BBr3), and borane (BH3) were found to react with ND substrates at room temperature in inert conditions. BBr3 and BCl3 were highly reactive with the diamond surface, and sheet-like structures were produced and verified with electron microscopy. Surface-sensitive spectroscopies were used to probe the molecular and atomic structure of the ND constructs' surface, and quantification showed the boron shell was less than 1 nm thick after 1-24 h reactions. Observation of the reaction supports a self-terminating mechanism, similar to atomic layer deposition growth, and is likely due to the quenching of alcohols on the diamond surface. X-ray absorption spectroscopy revealed that boron-termination generated midgap electronic states that were originally predicted by density functional theory (DFT) several years ago. DFT also predicted a negative electron surface, which has yet to be confirmed experimentally here. The boron-diamond nanostructures were found to aggregate in dichloromethane and were dispersed in various solvents and characterized with dynamic light scattering for future cell imaging or cancer therapy applications using boron neutron capture therapy (BNCT). The unique templating mechanism based on nucleophilic alcohols and electrophilic trigonal precursors allows for covalent bond formation and will be of interest to researchers using diamond for quantum sensing, additive manufacturing, BNCT, and potentially as an electron emitter.

Unusual S=1 Four‐Coordinate Fe(IV) Complexes Supported by Bisamide Ligands: Syntheses, Characterization, and Electronic Structures

AbstractThe catalytic relevance of Fe(IV) species in non‐heme iron catalysis has motivated synthetic advances in well‐defined five‐ and six‐coordinate Fe(IV) complexes for a better understanding of their fundamental electronic structures and reactivities. Herein, we report the syntheses of FeDipp2 and FeMes2, a pair of unusual four‐coordinate non‐heme formally Fe(IV) complexes with S=1 ground states supported by strongly donating bisamide ligands. By combining spectroscopic characterization and computational modeling, we found that small variations in ligand aryl substituents resulted in substantial changes in both structures and bonding. This work highlights the strong donor capabilities and modularity of the bisamide ligand set. More broadly, it is a critical contribution to the utilization of ligand design to modulate molecular geometries and electronic structures of low‐coordinate, high‐valent iron complexes.

Unusual S = 1 Four-Coordinate Fe(IV) Complexes Supported by Bisamide Ligands: Syntheses, Characterization, and Electronic Structures.

The catalytic relevance of Fe(IV) species in non-heme iron catalysis has motivated synthetic advances in well-defined five- and six-coordinate Fe(IV) complexes for a better understanding of their fundamental electronic structures and reactivities. Herein, we report the syntheses of FeDipp2 and FeMes2, a pair of unusual four-coordinate non-heme formally Fe(IV) complexes with S = 1 ground states supported by strongly donating bisamide ligands. By combining spectroscopic characterization and computational modeling, we found that small variations in ligand aryl substituents resulted in substantial changes in both structures and bonding. This work highlights the strong donor capabilities and modularity of the bisamide ligand set. More broadly, it is a critical contribution to the utilization of ligand design to modulate molecular geometries and electronic structures of low-coordinate, high-valent iron complexes.

Biodegradable and biocompatible nonisocyanate polyurethanes synthesized from bio-derived precursors

Despite the enormous use of polyurethanes (PUs) in multiple aspects of modern lifestyle, the industrial scale manufacturing of PUs uses toxic chemicals like isocyanates, phosgene till today. In addition, the non-biodegradability and non-biocompatibility of PUs and their debris are serious cause of concerns for the environment. To deal with these challenges, in the current work, a new approach is reported in which bio-derived non-isocyanate polyurethanes were synthesized by exploiting viable amino acid-based diamines and biscyclocarbonates from sebacoyl chloride and diglycerol derivatives in a readily doable process. The newly designed polyhydroxyurethanes (PHUs) exhibited remarkable biodegradability and biocompatibility (cell viability) in comparison with commercial diamine based PHUs. A series of PHUs were synthesized in bulk and solvent free green synthetic route by polycondensing library of amino acids (such as glycine, alanine, valine, and isoleucine etc.) based diamines consisting of varying alkyl chain lengths and biscyclocarbonates like sebacic biscyclocarbonate and diglycerol biscyclocarbonate etc. All the synthesized PHUs were thoroughly characterised by IR, NMR and HRMS spectroscopic techniques. The impact of chain length and molecular structure of the synthesized PHUs were also evaluated using DSC, TGA, SEC, water contact angle measurements and hydrolytic degradation studies. The molar masses of the PHUs obtained from the SEC analysis are in the range of ∼17,000–24,000 Da. The current study demonstrated that amino acids is one of the major degradation products and are biocompatible in in-vitro conditions. The PHUs and their degradable products showed excellent cell viability when studied in HEK293T cells that were carried out using microgram to milligram concentration of PHUs. The outcome of this work in comparison to conventional PHUs and polyurethanes clearly demonstrated good biocompatibility and hence drawing attention to potential applications in bio-adhesives, bio-implants, drug delivery, and green coatings etc. in the near future.

Effect of the Molecular Structure and Degree of Polymerization of Fructans on the Growth Behavior of Four Lactic Acid Bacteria

Effect of the Molecular Structure and Degree of Polymerization of Fructans on the Growth Behavior of Four Lactic Acid Bacteria

Development of a 2D Network of Zinc Organophosphate with an 8-Membered Ring Core Having Corrosion Resistance Properties.

A 2D framework, i.e., zinc organophosphate [Zn(tmbiph)(solv)]2 (tmbiphH4 = tetramethyl-[1,1'-biphenyl]-4,4'-diyl bis(dihydrogen phosphate); solv = 2H2O) with an eight-membered ring core has been developed. The hierarchical and rational design of the zinc organophosphate has been achieved by carefully designing an organic bisphosphate ligand with two phosphate monoester groups connected through extended aromatic rings with methyl groups at ortho positions. The development of the 2D network does not require any ancillary ligand due to participating two phosphate groups in the coordination. The molecular structure of the zinc phosphate material was determined using single-crystal X-ray diffraction technique. The corresponding Co and Cu organophosphate materials have also been obtained using the same synthetic method; however, these compounds could not be confirmed structurally due to nondiffractive crystal quality. The structure of zinc organophosphate obtained through single-crystal X-ray diffraction has also been supported by theoretical calculations using density function theory. Furthermore, the zinc organophosphate material has been employed as an corrosion inhibitor for mild steel. The effect of the zinc phosphate framework on mild steel in 1 M HCl was investigated using polarization and electrochemical impedance spectroscopy. This study suggests that such phosphate inhibitors can be employed in the form of a thin protective layer on the electrode surface.

Design of FDM fabricated poly-lactic acid parts with forced-air cooling speed as the new control parameter to tune its shape memory effect

Poly lactic acid (PLA) as one of the shape memory polymers has extensively been used as the material in the 3D printing by fused deposition modeling process. In this study, we introduced the forced-air cooling speed as new control parameter in the fabrication process. A commercial material extrusion printer was retrofitted with a control module of forced-air cooling system. The shape memory effects of the PLA printed in different cooling speeds from 0–5 m s−1 were first measured by submerging the printed coupon specimens into water bath at recovery temperature. It is found that the changes in dimensions were mainly anisotropic and dependent of the raster angle in printing, in addition to the controlled cooling speed. The shape memory strains were roughly in linear trend with the magnitude of cooling air speed. In other words, the shape memory effect of the PLA can be easily controlled by the cooling air speed in fabrication. X-ray diffraction measurement on the specimens before and after recovery treatment confirmed the shape memory effect was related to the partial crystallization of molecular structure. Moreover, the different cooling air speeds also induced different thermal stresses in the printed specimens which manifest its important role in the total shape memory strain. Finally, the proposed theoretical beam formulation for the recovery bending deflection was shown to have good prediction accuracy comparing with experimental measurements.

Quantitative structure‐property relationship techniques for predicting carbon dioxide solubility in ionic liquids using machine learning methods

AbstractIonic liquids (ILs) are considered unique and attractive types of solvents with great potential to capture carbon dioxide (CO2) and reduce its emissions into the atmosphere. On the other hand, carrying out experimental measurements of CO2 solubility for each new IL is time‐consuming and expensive. Whereas, the possible combinations of cations and anions are numerous. Therefore, the preparation and design of such processes requires simple and accurate models to predict the solubility of CO2 as a greenhouse gas. In the present study, two different models, namely: artificial neural network (ANN) and support vector machine optimized with dragonfly algorithm (DA‐SVM) were used in order to establish a quantitative structure–property relationship (QSPR) between the molecular structures of cations and anions and the CO2 solubility. More than 10 116 CO2 solubility data measured in various ionic liquids (ILs) at different temperatures and pressures were collected. 13 significant PaDEL descriptors (E2M, MATS8S, TDB6I, TDB1S, ATSC4V, MATS8M, ATSC7V, Gats2S, Gats5S, Gats5C, ATSC6V, DE, and Lobmax), temperature and pressure were considered as the model input data. For the test set data (2023 data point), the estimated mean absolute error (MAE) and R2 for the ANN model are of 0.0195 and 0.9828 and 0.0219 and 0.9745 for the DA‐SVM model. The results obtained showed that both models can reliably predict the solubility of CO2 in ILs with a slight superiority of the ANN model. Examination of sensitivity and outlier diagnosis examinations confirmed that the QSPR model optimized using the ANN algorithm is better suited to correlate and predict this property.

Optimizing Active Layer Morphology of Organic Solar Cells by Constructing Random Copolymers with Simple Third Units.

The molecular structure of the polymer PM6 is elaborately modified through random copolymerization by incorporating simple units of either difluoro-substituted thiophene (2FT) or dicyano-substituted thiophene (2CNT). The incorporation of the 2FT unit significantly enhanced the coplanarity of the random copolymers, leading to improved molecular crystallinity, whereas the introduction of the 2CNT unit featured the opposite effect. Thanks to the optimized morphology resembling a fiber-like interpenetrating network structure, the organic solar cells based on PM6-10%2FT:IT4F showed higher and more balanced charge mobilities, achieving a power conversion efficiency (PCE) of 12.65%, which is comparable to that of PM6-based devices. For comparison, the 2CN-series random copolymers-based devices exhibited lower PCEs of ˂12%. Interestingly, a superior PCE close to 19.0% is achieved in PM6:L8-BO:PM6-20%2CN based ternary device due to the significant improvement in open-circuit voltage. This work demonstrates that the crystallinity of donor polymers can be enhanced by introducing simple structural units to strengthen the coplanarity of the backbone, thereby achieving an optimized morphology that promotes favorable charge transport.

Combined DFT and Monte Carlo simulation studies of potential corrosion inhibition properties of coumarin derivatives.

Corrosion, the degradation of materials due to chemical reactions with their environment presents significant challenges both economically and environmentally. It affects various industries, including construction, transportation, and manufacturing, leading to equipment failures, safety hazards, and increased maintenance costs. Coumarin derivatives have shown promise due to their inherent chemical properties and potential for biodegradability. In this study, a series of the coumarin derivatives were examined in silico to reveal their potential corrosion inhibition properties toward the Fe(110) and Cu(111) surfaces. The compounds investigated include coumarin (2H-chromen-2-one, 1), furanocoumarin (7H-furo[3,2-g]chromen-7-one, 2), dihydrofurano coumarin (2,3-dihydro-7H-furo[3,2-g]chromen-7-one, 3), pyrano coumarin-linear type (8,8-dimethyl-2H,8H-pyrano[3,2-g]chromen-2-one, 4), pyrano coumarin-angular type (8,8-dimethyl-2H,8H-pyrano[2,3-f]chromen-2-one, 5), bicoumarin (3,3'-methylenebis(2H-chromen-2-one), 6), and phenyl coumarin (4-phenyl-2H-chromen-2-one, 7). The findings suggest that the bicoumarin derivative 6 exhibits the lowest adsorption energy with the Fe(110) surface, while the same energy absolute value is about two times lower for the Cu(111) surface. This is due to the formation of a planar configuration of a molecule of 6 on the metal surfaces with the participation of both coumarin fragments upon interacting with the Fe(110) surface, while one coumarin fragment interacts with the Cu(111) surface. Density functional theory (DFT) calculations were employed to study the electronic properties of the coumarin derivatives. The specific computational method used was B3LYP, a hybrid functional that combines with the 6-311 + + G(d,p) basis set. Each coumarin derivative was first subjected to a geometry optimization to find the most stable molecular structure. Electronic properties, dipole moments, and molecular electrostatic potential surfaces were calculated. The Monte Carlo simulations were used to model the adsorption behavior of the coumarin derivatives on metal surfaces, namely, Fe(110) and Cu(111). These simulations allowed to visualize interaction of the studied molecules with the metal surfaces, which is crucial for their function as corrosion inhibitors. The present study provides a comprehensive understanding of the corrosion inhibition potential of the applied coumarin derivatives. The insights gained from these methods can inform the development of effective, sustainable corrosion inhibitors that are both environmentally friendly and highly efficient.

Spirocyclic pyrrolidinyl nitroxides with exo-methylene substituents.

Nitroxides are stable organic radicals with exceptionally long lifetimes, which render them uniquely suitable as observable probes or polarising agents for spectroscopic investigation of biomolecular structure and dynamics. Radical-based probes for biological applications are ideally characterized by both robustness towards reductive degradation and beneficial electron spin relaxation parameters. These properties are largely influenced by the molecular structure of the nitroxide scaffold, and also by the conformations it prefers to adopt. In this study we present the synthesis of the first nitroxides based on a spirocyclic pyrrolidine scaffold with an exocyclic methylene substituent. The conformations adopted by these nitroxides were evaluated by X-ray crystallography, both with single nitroxide crystals and by inclusion of nitroxides in a microporous crystalline sponge. The kinetic and thermodynamic stability of the new nitroxides towards reduction was investigated by electron paramagnetic resonance (EPR) spectroscopy and cyclic voltammetry (CV). In combination with EPR measurements of electron spin relaxation properties, these results suggest that this new family of nitroxides can provide access to multifunctionalized probes and polarising agents suitable for use in biological environments at elevated temperatures.

The Perfluoro‐o‐phenylene‐mercury Trimer [Hg(o‐C6F4)]3 – a Textbook Example of Phase‐Dependent Structural Differences

AbstractThe geometric and electronic structure of [Hg(o‐C6F4)]3 (1) in the gas phase, i. e. free of intermolecular interactions, was determined by a synchronous gas‐phase electron diffraction/mass spectrometry experiment (GED/MS), complemented by quantum chemical calculations. 1 is stable up to 498 K and the gas phase contains a single molecular form: the trimer [Hg(o‐C6F4)]3. It has a planar structure of D3h symmetry with a Hg–C distance of 2.075(5) Å and a Hg–Hg distance of 3.614(7) Å (both rh1). Structural differences between the crystalline and gaseous state have been analyzed. Different DFT functional‐basis combinations were tested, demonstrating the importance to consider the relativistic effects of the mercury atoms. The combination PBE0/MWB(Hg),cc‐pVTZ(C,F) turned out to be the most appropriate for the geometry optimization of such organomercurials. The electronic structure of 1, the nature of the chemical bonding in C−Hg−C fragments and the nature of the Hg⋅⋅⋅Hg interactions have been analyzed in terms of the Natural Bond Orbital (NBO) and Quantum Theory of Atoms in Molecules (QTAIM) approaches. The influence of the nature of halogen substitution on the structure of the molecules in the series [Hg(o‐C6H4)]3, [Hg(o‐C6F4)]3, [Hg(o‐C6Cl4)]3, [Hg(o‐C6Br4)]3 was also analyzed.