Mass Spectrometric Measurements Research Articles

Fragmentation and Isomerization Pathways of Natural and Synthetic Cannabinoids Studied via Higher Collisional Energy Dissociation Profiles

Cannabinoid molecules are the family of molecules that bind to the cannabinoid receptors (CB1 and CB2) of the human body and cause changes in numerous biological functions including motor coordination, emotion, and pain reception. Cannabinoids occur either naturally in the Cannabis Sativa plant or can be produced synthetically in the laboratory. The need for accurate analytical methods for analyzing cannabinoid molecules is of considerable current importance due to demands for detecting illegal cannabinoids and for monitoring the manufacture of popular, non-illegal cannabinoid products. Mass spectrometry has been shown to be an optimum technique for identifying cannabinoids. In this work, we perform Higher Collisional Dissociation (HCD) mass spectrometric measurements on an Orbitrap Fusion Tribrid Mass Spectrometer to measure the collision-energy-dependent molecular fragmentation pathways of a group of key cannabinoids and their metabolites (cannabidiol, Δ9-Tetrahydrocannabinol, 11-Hydroxy-Δ9-tetrahydrocannabinol, 11-nor-9-Carboxy-Δ9-tetrahydrocannabinol, cannabidiolic acid, tetrahydrocannabinolic acid), along with two synthetic cannabinoids (JWH-018 and MDMB-FUBINACA). This is the first time that cannabinoid molecules have been studied using energy-resolved HCD methods. We identified a number of common, primary fragmentation pathways, including loss of water, loss of other small neutral molecule units (e.g., butene), and rupture of the central C-C bond that links the aromatic and alkyl ring groups. Quantum chemical calculations are presented to provide insights into preferred protonation sites and to characterize isomerization of protonated open-ring cannabinoids (e.g., [CBDA + H]+) into closed-ring analogues (e.g., [THCA + H]+). A key result to emerge from our study is that energy-resolved HCD measurements are particularly valuable in identifying isomerization, since the isobaric pairs of molecular ions studied here (e.g., [CBDA + H]+ and [THCA + H]+) are associated with identical HCD profiles indicating that isomerization of one structure into the other has occurred during the electrospray–mass spectrometry process. This is an important result as it will have general applicability to other tautomeric ions and thus demonstrates the application of energy-resolved HCD as a tool for identifying tautomerization proclivity.

Shift of nanodroplet and nanocluster size distributions induced by dopant pick-up statistics.

In pick-up experiments using nanodroplet and nanocluster beams, the size distribution of hosts carrying a specified number of dopants changes when the vapor density in the pick-up region is altered. This change, analyzed here, has quantitative consequences for the interpretation of data that are sensitive to host size, such as mass spectrometric, spectroscopic, and deflection measurements.

Production, Isolation, and Characterization of Stable Isotope-Labeled Standards for Mass Spectrometric Measurements of Oxidatively-Damaged Nucleosides in RNA.

RNA undergoes oxidatively induced damage in living organisms analogous to DNA. RNA is even more vulnerable to damage than DNA due to its greater abundance, single-strandedness, lack of repair and chromatin proteins shield, and instability, among other effects. RNA damage can adversely affect gene expression, leading to protein synthesis alterations, cell death, and other detrimental biological consequences. Growing indications suggest the involvement of oxidatively induced RNA damage in the pathogenesis of various human diseases, aging, and age-related diseases. Oxidatively induced damage can cause modifications to all four heterocyclic bases in RNA. Precise measurement of such modifications in RNA is essential for understanding the biological effects of oxidatively induced RNA damage. In the past, mass spectrometry has been used for this purpose. In mass spectrometric measurements, the use of stable isotope-labeled analogues of analytes as internal standards is essential for accurate quantifications. Past work utilized a stable isotope-labeled analogue of 8-hydroxyguanosine only as an internal standard. Thus, far, no stable isotope-labeled analogues of other oxidatively modified RNA nucleosides were available. In the present work, we report on the preparation, isolation, and characterization of the 13C- and 15N-labeled analogues of a variety of modified pyrimidine- and purine-derived RNA nucleosides. We also show the application of these internal standards for the measurement of oxidatively induced RNA damage in several commercially available RNA samples and in DNA along with DNA damage.

Distribution of plutonium and radium in the human heart.

Since 1968, the United States Transuranium and Uranium Registries (USTUR) has studied the biokinetics and tissue dosimetry of uranium and transuranium elements in nuclear workers. As part of the USTUR collaboration with the Million Person Study (MPS) of Low-Dose Health Effects, radiation dose to different parts of the human heart is being estimated for workers with documented intakes of 239Pu or 226Ra. The study may be expanded for workers with intakes of 238U and other radionuclides. The distribution of radionuclides, expressed in terms of concentration (Bq per kg of tissue) serves as an important parameter for estimating radiation dose. Based on available organs from workers who donated their bodies or tissues for research, nine undissected hearts were selected: seven from USTUR registrants with plutonium exposure (males) and two individuals with radium intakes (female and male). For the plutonium workers, estimated 239Pu systemic deposition ranged from <74 Bq to 1765 Bq. Estimated 226Ra 'initial systemic intakes' were 10.1 MBq and 14.8 kBq for the female patient and male worker, respectively. Organ dissection was based on a heart model published by Borrego et al (2019). This model includes nine cardiac substructures: aorta, left main coronary artery, left atrium, left anterior descending artery, left circumflex artery, left ventricle, right atrium, right coronary artery, and right ventricle. In addition, heart valves, fat attached to epicardium, fluids, and a coronary bypass graft were collected resulting in 111 samples that are currently undergoing radiochemical analyses and mass-spectrometric measurements. The 239Pu and 226Ra evaluations are not completed. The results of this study are intended to support radiation worker health studies by improving associated dosimetric and epidemiological models.

Synthesis of Silicon in the Interaction of Aluminum With a Quasi-Neutron and Estimation of the Contribution of the Aluminum Hydride Complex

Among the nuclear fusion reactions of new elements, the simplest reaction refers to the capture of a proton p by the nucleus of the original element ZXA with the formation of the Z + 1YA+1 nucleus (Z and A are the charge and mass number of the element X). In the case of cold fusion, the occurrence of such a reaction is associated with the existence of quasi-neutron (p + e) states in which the proton is “escorted” by the electron e: ZXA + (p + e) ! Z + 1YA+1 + e. For example the synthesis of zinc from copper was established. It is important to note that the ratios of the proportions of synthesized isotopes in most cases should differ significantly from natural ratios, which would certainly confirm their artificial origin. The data of preliminary mass spectrometric measurements for the synthesis of zinc from copper, gallium from zinc, and rhenium from tungsten are consistent with this conclusion. However, for relatively heavy elements, the masses of daughter atoms with Z + 1YA+1 nuclei are difficult to distinguish from the masses of hydride complexes of parent atoms with ZXA nuclei and hydrogen atoms H formed in the course of mass spectrometric measurements. In this regard, the problem of estimating the contributions of daughter atoms and hydride complexes is topical. The solution of this problem was carried out for the case of silicon synthesis from aluminum. In an air environment with water vapor, an electric arc was ignited between an aluminum anode and a tungsten cathode. Aluminum has one stable isotope 13Al27; therefore, the synthesis of only one of the three stable silicon isotopes 14Si28 was expected, which was observed in the mass spectrum of the powder formed on the anode surface (peak at ⇡ 27.977 a.m.u.). The AlH complex corresponds to a peak at ⇡ 27.989 a.m.u. This peak has a height approximately 2.5 times less than the height of the peak for the mass distribution of silicon atoms. Thus, the relatively low intensity for the mass distribution of the AlH complex suggests that it is the isotope ratios of the synthesized daughter nuclei that make the main contributions to the observed isotope mass ratios in the cases of parent atoms having several stable isotopes.

Measuring 15N and 13C Enrichment Levels in Sparsely Labeled Proteins Using High-Resolution and Tandem Mass Spectrometry.

Isotope labeling of both 15N and 13C in selected amino acids in a protein, known as sparse labeling, is an alternative to uniform labeling and is particularly useful for proteins that must be expressed using mammalian cells, including glycoproteins. High levels of enrichment in the selected amino acids enable multidimensional heteronuclear NMR measurements of glycoprotein three-dimensional structure. Mass spectrometry provides a means to quantify the degree of enrichment. Mass spectrometric measurements of tryptic peptides of a selectively labeled glycoprotein expressed in HEK293 cells revealed complicated isotope patterns which consisted of many overlapping isotope patterns from intermediately labeled peptides, which complicates the determination of the label incorporation. Two challenges are uncovered by these measurements. Metabolic scrambling of amino groups can reduce the 15N content of enriched amino acids or increase the 15N in nontarget amino acids. Also, undefined, unlabeled medium components may dilute the enrichment level of labeled amino acids. The impact of this unexpected metabolic scrambling was overcome by simulating isotope patterns for all isotope-labeled peptide states and generating linear combinations to fit to the data. This method has been used to determine the percent incorporation of 15N and 13C labels and has identified several metabolic scrambling effects that were previously undetected in NMR experiments. Ultrahigh mass resolution is also utilized to obtain isotopic fine structure, from which enrichment levels of 15N and 13C can be assigned unequivocally. Finally, tandem mass spectrometry can be used to confirm the location of heavy isotope labels in the peptides.

Mechanistic Insights into the cis-Selective Catalytic Ring-Opening Metathesis Polymerization.

Cis-selective ring-opening metathesis polymerization (ROMP) with the commercial Grubbs "nitrato catalyst" has shown promise for synthesizing stereoregular materials, but it comes with the drawback of losing control over the molecular weight due to the poor initiation rate of the catalyst and the need for stoichiometric ruthenium complex loading. To address these issues, we developed a chain transfer polymerization method that allows for the catalytic synthesis of polymers while controlling the degree of polymerization. This allowed us to produce shorter polymers with exceptional chain-end control. Analysis of the polymers revealed a novel double monomer addition mechanism for this catalyst. MALDI-ToF mass spectrometric measurements showed that when using small monomers like norbornene, the polymer chains contained only odd numbers of monomers. In contrast, the polymerization of norbornene-imide-type monomers shows a major distribution with odd numbers of monomers along with a minor distribution of even numbers. This unique distribution of polymer chain types had not been previously observed in ROMP. We explain this phenomenon by the chiral nature of the catalyst that yields two isomeric catalytic species with dissimilar reactivities toward monomer and chain transfer agents.

Krypton-85 chronometry of spent nuclear fuel

Abstract. We describe the use of the radionuclide 85Kr, which is produced by nuclear fission and has a half-life of 10.76 years, to determine the age of spent nuclear fuel. The method is based on mass-spectrometric measurement of the relative abundance of fissiogenic Kr isotopes extracted from a fuel sample, and we show that it can be applied to micron-scale particles of spent fuel that are analogous to particles that have been released into the environment from various nuclear facilities in the past. 85Kr chronometry is potentially valuable for identifying and attributing nuclear materials, grouping samples into collections of common origin that can be used to reconstruct the origin and irradiation history of the material, and verifying declared nuclear activities in the context of international monitoring programs.

Methanol steam reforming over copper supported on apatites

Low-temperature methanol steam reforming (MSR) over Cu is an efficient process for releasing H2 from this promising liquid hydrogen carrier but the Cu contents of commercial catalysts are often exceedingly high. Here we show that Sr-exchanged fluoro and hydroxyapatites with 1 wt% Cu exhibit very high methanol turnover frequencies up to 386 h−1 and H2 production rates up to 6569 mol H2 kgCu−1 h−1 with CO selectivity as low as ∼0.25 % at 250 °C. Formaldehyde and methyl formate are the only other byproducts which are especially observed over catalysts with low Sr/P ratio in the hydroxyapatite. The reforming proceeds through methoxy, formaldehyde and formate species according to in situ FTIR and mass spectrometric measurements. The spectroscopic analyses further reveal the involvement of apatitic HPO42- ions in the catalytic sequence. Thus, the catalytic synergy between Cu and apatites provides a basis for highly efficient, bifunctional MSR catalysts with low copper content.

A new multi-analytical procedure for radiocarbon dating of historical mortars

The overarching challenge of this research is setting up a procedure to select the most appropriate fraction from complex, heterogeneous materials such as historic mortars in case of radiocarbon dating. At present, in the international community, there is not a unique and fully accepted way of mortar sample preparation to systematically obtain accurate results. With this contribution, we propose a strategy for selecting suitable mortar samples for radiocarbon dating of anthropogenic calcite in binder or lump. A four-step procedure is proposed: (I) good sampling strategies along with architectural and historical surveys; (II) mineralogical, petrographic, and chemical characterization of mortars to evaluate the feasibility of sample dating; (III) a non-destructive multi-analytical characterization of binder-rich portions to avoid geogenic calcite contamination; (IV) carbonate micro-sample preparation and accelerator mass spectrometer (AMS) measurements. The most innovative feature of the overall procedure relies on the fact that, in case of positive validation in step III, exactly the same material is treated and measured in step IV. The paper aims to apply this procedure to the ancient mortar of the Florentine historical building (Trebbio Castle), selecting micro-samples suitable for dating in natural hydraulic mortars. The discussion of the mortar dating results with the historical-archaeological hypotheses provided significant insights into the construction history of the building.

Simulation Study of Crystalline Al2O3 Thin Films Prepared at Low Temperatures: Effect of Deposition Temperature and Biasing Voltage

In this paper, classical molecular dynamics simulations were used to explore the impact of deposition temperature and bias voltage on the growth of Al2O3 thin films through magnetron sputtering. Ion energy distributions were derived from plasma mass spectrometer measurements. The fluxes of deposited particles (Ar+, Al+, and O−) were categorized into low, medium, and high energies, and the results show that the films are dominated by amorphous Al2O3 at low incident energies without applying bias. As the deposition temperature increased, the crystallinity of the films also increased, with the crystals predominantly consisting of γ-Al2O3. The crystal content of the deposited films increased when biased with −20 V compared to when no bias was applied. Crystalline films were successfully obtained at a deposition temperature of 773 K with a −20 V bias. When biased with −40 V, crystals could be obtained at a lower deposition temperature of 573 K. Increasing the bias enables the particles to have higher energy to overcome the nucleation barrier of the crystallization process, leading to a greater degree of film crystallization. At this stage, the average bond length between Al-O is measured to be approximately 1.89 Å to 1.91 Å, closely resembling that of the crystal.

The Fe-MAN Challenge: Ferrates-Microkinetic Assessment of Numerical Quantum Chemistry.

Organometallic species, such as organoferrate ions, are prototypical nucleophiles prone to reacting with a wide range of electrophiles, including proton donors. In solution, the operation of dynamic equilibria and the simultaneous presence of several organometallic species severely complicate the analysis of these fundamentally important reactions. This can be overcome by gas-phase experiments on mass-selected ions, which allow for the determination of the microscopic reactivity of the target species. In this contribution, we focus on the reactivity of a series of trisarylferrate complexes toward 2,2,2-trifluoroethanol and 2,2-difluoroethanol. By means of mass-spectrometric measurements, we determined the experimental bimolecular rate constants kexp of the gas-phase protolysis reactions of the trisarylferrate anions FePh3- and FeMes3- with the aforementioned acids. Based on these experiments, we carried out a dual blind challenge, inviting theoretical groups to submit their best predictions for the activation barriers and/or theoretical rate constants ktheo. This provides a unique opportunity to evaluate different computational protocols under minimal bias and sets the stage for further benchmarking of quantum chemical methods and data-driven approaches in the future.

Understanding secondary particles in a regional site of Yangtze River Delta: Insights from mass spectrometric measurement

Submicron particulate matter (PM1) poses significant risks to health risks and global climate. In this study, secondary organic aerosols (SOA) and inorganic compositions were examined for their physicochemical characteristics and evolution using high-resolution aerosol instruments in Changzhou over one-month period. The results showed that transport accompanied by regional static conditions leaded to the occurrence of heavy pollution. In addition, regional generation and local emissions also leaded to the occurrence of light and moderate pollution during the observation period in Changzhou. Organic aerosols (OA) and nitrate (NO3−) accounted for 45 % and 23 % of PM1, respectively. The increase in PM1 was dominated by the contribution of NO3− and OA. SOA was dominance in OA (63 % with 40 % MO-OOA), which was higher than primary organic aerosols (POA). Besides, photochemical reactions and the high oxidizing nature of the urban atmosphere promoted the production of OA, especially MO-OOA in Changzhou. Our results highlight that secondary particles contribute significantly to PM pollution in Changzhou, underlining the importance of controlling emissions of gaseous precursors, especially under high oxidation conditions.

The saline infusion test with mass spectrometric measurements of aldosterone in patients tested for primary aldosteronism

The saline infusion test with mass spectrometric measurements of aldosterone in patients tested for primary aldosteronism

Fast and Accurate Disulfide Bridge Detection

Recombinant expression of proteins, propelled by therapeutic antibodies, has evolved into a multibillion dollar industry. Essential here is the quality control assessment of critical attributes, such as sequence fidelity, proper folding, and posttranslational modifications. Errors can lead to diminished bioactivity and, in the context of therapeutic proteins, an elevated risk for immunogenicity. Over the years, many techniques were developed and applied to validate proteins in a standardized and high-throughput fashion. One parameter has, however, so far been challenging to assess. Disulfide bridges, covalent bonds linking two cysteine residues, assist in the correct folding and stability of proteins and thus have a major influence on their efficacy. Mass spectrometry promises to be an optimal technique to uncover them in a fast and accurate fashion. In this work, we present a unique combination of sample preparation, data acquisition, and analysis facilitating the rapid and accurate assessment of disulfide bridges in purified proteins. Through microwave-assisted acid hydrolysis, the proteins are digested rapidly and artifact-free into peptides, with a substantial degree of overlap over the sequence. The nonspecific nature of this procedure, however, introduces chemical background, which is efficiently removed by integrating ion mobility preceding the mass spectrometric measurement. The nonspecific nature of the digestion step additionally necessitates new developments in data analysis, for which we extended the XlinkX node in Proteome Discoverer to efficiently process the data and ensure correctness through effective false discovery rate correction. The entire workflow can be completed within 1 h, allowing for high-throughput, high-accuracy disulfide mapping.

On the simulation and interpretation of substrate-water exchange experiments in photosynthetic water oxidation.

Water oxidation by photosystem II (PSII) sustains most life on Earth, but the molecular mechanism of this unique process remains controversial. The ongoing identification of the binding sites and modes of the two water-derived substrate oxygens ('substrate waters') in the various intermediates (Si states, i = 0, 1, 2, 3, 4) that the water-splitting tetra-manganese calcium penta-oxygen (Mn4CaO5) cluster attains during the reaction cycle provides central information towards resolving the unique chemistry of biological water oxidation. Mass spectrometric measurements of single- and double-labeled dioxygen species after various incubation times of PSII with H218O provide insight into the substrate binding modes and sites via determination of exchange rates. Such experiments have revealed that the two substrate waters exchange with different rates that vary independently with the Si state and are hence referred to as the fast (Wf) and the slow (WS) substrate waters. New insight for the molecular interpretation of these rates arises from our recent finding that in the S2 state, under special experimental conditions, two different rates of WS exchange are observed that appear to correlate with the high spin and low spin conformations of the Mn4CaO5 cluster. Here, we reexamine and unite various proposed methods for extracting and assigning rate constants from this recent data set. The analysis results in a molecular model for substrate-water binding and exchange that reconciles the expected non-exchangeability of the central oxo bridge O5 when located between two Mn(IV) ions with the experimental and theoretical assignment of O5 as WS in all S states. The analysis also excludes other published proposals for explaining the water exchange kinetics.

Cooking emissions are a major source of racial-ethnic air pollution exposure disparities in the United States

Racial-ethnic minority populations in the US are disproportionately exposed to airborne fine particulate matter (PM2.5), but few national studies have focused individually on the sources that contribute to these disparities. We address this gap by conducting a comprehensive analysis of PM2.5 exposure disparities by race-ethnicity in the US, focusing on three source-categories: mobile-sources, cooking, and all other sources combined. Our approach is based on high-resolution, national land-use regression estimates of source-resolved PM2.5 components, derived from high-resolution aerosol mass spectrometer measurements. We find that each of these sources contributes approximately one-third of the overall PM2.5 exposure disparities by race-ethnicity. While the importance of mobile-source tailpipe emissions is well recognized, our study underscores the significance of cooking emissions in creating PM2.5 exposure disparities. This finding represents a potentially significant opportunity to reduce these disparities, as cooking emissions are currently largely unregulated. It has important implications for policymakers and public health advocates aiming to address the persistent issue of racial-ethnic disparities in air pollution.

Fission-track age calibration: Phi and Zeta, never the twain shall meet?

The fission-track method was intended to be an autonomous dating method requiring two track counts and a neutron fluence measurement. It became clear that it was beset with methodological problems, and neutron fluence measurements were abandoned in favour of age standards. The coming of mass-spectrometric uranium measurements eliminated the need for irradiations altogether, and stimulated renewed efforts to establish fission-track dating as an autonomous method. This ran into similar problems as before, and recent publications signal a return to age standards. The attempts at independent dating nevertheless revealed that experts agree on the recommended fission constant and the need to consider experimental factors related to the track counts. In spite of that, the renewed reliance on standards makes that fission-track ages are again not independent, but relative, ages with an uncertain meaning, and from their nature untestable.We report an attempt at standardless and standard-based dating of the Durango and Duluth apatites using neutron irradiation and the external detector method. We start from the assumption that neutron fluence measurements are the most precise and accurate achievable in fission-track dating, a consensus on the recommended fission constant, and on the need to consider experimental factors. One factor (ζ0) accounts for the combined experimental influences; ζ0 can be calculated from identifiable contributions related to track registration, etching and counting; ζ0 can also be determined by experiment and calculated from the ages of standards. This gives three separate, consistent, dimensionless calibration factors that, in contrast to Z and ζ, are independent of the neutron fluence or the uranium content of a reference glass; ζ0 remains a personal factor, however.The standardless fission-track ages of the Durango age standard are in agreement with its reference age and the standardless and standard-based ages of the Duluth apatites are consistent with each other. Furthermore, if ζ0 is used to correct conventional Z- (and by implication ζ-) values for experimental effects, the results are consistent with their definitions in terms of physical parameters. Although ζ0 is a personal factor, the small number of measurements to date is consistent with each other. In contrast, annealing corrections based on the fossil and induced confined fission track lengths overestimate the reference age of Durango and produce incompatible standardless and standard-based ages of the dated apatites. We argue that this points to unresolved issues with the relationship between the age and the fossil track length, and suggest a connection with etching.Plots of the single-grain ages against uranium content and radial plots of the data exhibit conspicuous structure. However statistical factors alone account for the nature and magnitude of the observed correlations. This implies that in the case of the Duluth apatites there is no identifiable effect of radiation damage on the single-grain ages despite their high accumulated α-doses and protracted thermal histories. Spurious correlations must be addressed before attempting to interpret the observed data structure in terms of radiation damage, apatite composition or age components.

Investigation of oil emission mechanisms in a marine medium-speed dual-fuel engine

Pilot-ignition Otto marine engines are known for greatly reduced emissions of air pollutants (sulphur oxides, nitrogen oxide, particulates) compared to marine diesel engines. However, lubricating oil emissions still are about one order of magnitude higher than in land-based systems. To identify reduction potentials, a better understanding of oil emission mechanisms has to be gained. For this purpose, mass spectrometric oil emission measurements and fluorescence lubricating film thickness measurements were performed on a medium-speed marine engine. With the fluorescence measuring system, the varying lubricating oil film on the cylinder wall can be visualised and analysed in sub-crank-angle resolution. By applying the developed calibration method to the measurement data, the oil film thickness can be determined in µm. It is shown that the oil film left by the piston rings on the liner as it moves down is almost halved after ignition compared to during intake stroke. The authors have further been able to detect and time operating point dependent ring rotation and investigations show a connection between ring rotation and cylinder liner temperature distribution. Aligning ring gaps allow blow-by to happen. This and other high intensity events such as engine knock, load shedding or the transition from diesel-mode to gas-mode, heavily disturb the oil layer and cause peaking oil emissions.

Copper(II) complexes with N,O-coordinating thiopseudoureas: syntheses, structures, and properties

Syntheses, characterization, and physical properties of two complexes of copper(II) having the general molecular formula [Cu(L n )2] (1 and 2) with benzyl-N′-(4-R-benzoyl)-N-(2,6-diisopropylphenyl)carbamimidothioates (HL n , where n = 1 and 2 for R = H and Cl, respectively) are reported. Both complexes were characterized by mass spectrometric, magnetic susceptibility, and various spectroscopic (IR, UV–Vis, and EPR) measurements. The molecular structures of 1 and 2 were established by single crystal X-ray crystallographic studies. In each complex, the bivalent metal center is in a near perfect square-planar trans-N2O2 coordination environment assembled by two bidentate six-membered chelate rings forming iminolate-O and azomethine-N donor (L n )− ligands. In the crystal lattice, the packing of 1 is according to the symmetry operations, while intermolecular π⋯π and C–H⋯π interactions assisted self-assembly of 2 leads to a two-dimensional sheet-like structure. Mass spectrometric and infrared and electronic spectroscopic data are in agreement with their molecular formulas and similar structures. The room temperature magnetic moments and EPR spectra of both complexes are consistent with the S = ½ ground state and the square-planar coordination geometry of the metal ion in each complex.