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DOE OSTI2026

Concerted Proton–Electron Transfer Minimizes Substituent Effects on Adsorbed Phthalocyanine Electrocatalysis

Molecularly modified electrodes (MMEs) are potent electrocatalysts, but few principles exist for their rational design. Electrocatalysis by soluble molecules depends strongly on substituents that tune the catalyst redox potential (E 1/2 ), but it is unclear if this parameter similarly impacts MME catalysis. Herein, we employ the hydrogen evolution reaction (HER) as a test case for comparing carbon-adsorbed cobalt phthalocyanine (CoPc/C) and cobalt hexadecafluoro-phthalocyanine (CoFPc/C). By correlating HER activity and voltammetric data to total Co surface concentration across a wide range of catalyst loadings, we find that only 5–25% of adsorbed Co sites contribute to the Co(II/I) redox wave and that this subpopulation poorly correlates with catalytic activity. Instead, in the low-loading limit, catalytic activity correlates linearly with the majority Co(II/I)-silent Co population, revealing per-site turnover frequency (TOF) values for HER. Despite a 230 mV difference in Co(II/I) redox potentials, CoPc/C and CoFPc/C display TOF values differing by less than a factor of 3 when compared over a wide potential range. Mechanistic studies point to an inner-sphere concerted proton–electron transfer step as rate-determining, suggesting that the Co–H bond dissociation free energy (BDFE) rather than the Co(II/I) E 1/2 is thermodynamically relevant. Computational studies indicate that the fluoro-substituents lead to compensatory changes in Co(II/I) E 1/2 and Co(I) basicity, leaving the Co–H BDFE largely unchanged between CoPc and CoFPc and thereby manifesting in similar catalytic rates. Furthermore, these results highlight the limited effect of E 1/2 -tuning on MME catalytic activity and motivate the development of methods to directly alter active site–substrate BDFE.

Catalysts↗

DOE OSTI2024

Distinguishing the XUV-induced Coulomb explosion dynamics of iodobenzene using covariance analysis

The primary and secondary fragmentation dynamics of iodobenzene following its ionization at 120 eV were determined using three-dimensional velocity map imaging and covariance analysis. Site-selective iodine 4d ionization was used to populate a range of excited polycationic parent states, which primarily broke apart at the carbon-iodine bond to produce I+ with phenyl or phenyl-like cations (C n H x + or C n H, with n = 1 – 6 and x = 1 – 5). The molecular products were produced with varying degrees of internal excitation and dehydrogenation, leading to stable and unstable outcomes. This further allowed the secondary dynamics of C 6 H x 2+ intermediates to be distinguished using native-frame covariance analysis, which isolated these processes in their own centre-of-mass reference frames. Furthermore, the mass resolution of the imaging mass spectrometer used for these measurements enabled the primary and secondary reaction channels to be specified at the level of individual hydrogen atoms, demonstrating the ability of covariance analysis to comprehensively measure the competing fragmentation channels of aryl cations, including those involving intermediate steps.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2025

Photoinduced electronic excitations drive polymerization of carbon monoxide: A first-principles study

Under pressure, carbon monoxide (CO) transforms into a polymer that can be recovered to ambient conditions. While this transformation can occur without additional stimuli, experimental observations have shown that laser irradiation can induce a similar transformation at reduced pressure. The resulting polymeric phase, which is metastable under ambient conditions, releases energy through decomposition into more stable configurations. Using time-dependent density functional theory and Born–Oppenheimer molecular dynamics simulations, we investigate the mechanism by which electronic excitation facilitates CO polymerization. Our calculations reveal that electronic excitation enhances carbon–carbon bonding, enabling polymerization at pressures significantly lower than those required by conventional compression methods. In conclusion, these findings suggest that a photo-assisted approach could be employed to synthesize novel, potentially energetic materials under less demanding pressure conditions.

Born-Oppenheimer molecular dynamics↗

DOE OSTI2025

Building molecular model series from heterogeneous CryoEM structures using Gaussian mixture models and deep neural networks

Cryogenic electron microscopy (CryoEM) produces structures of macromolecules at near-atomic resolution. However, building molecular models with good stereochemical geometry from those structures can be challenging and time-consuming, especially when many structures are obtained from datasets with conformational heterogeneity. Here we present a model refinement protocol that automatically generates series of molecular models from CryoEM datasets, which describe the dynamics of the macromolecular system and have near-perfect geometry scores. This method makes it easier to interpret the movement of the protein complex from heterogeneity analysis and to compare the structural dynamics observed from CryoEM data with results from other experimental and simulation techniques.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2025

Molecular Modifications of Crystalline Poly(triazine imide) for Advancing Its Structure–Property Relationships in Light-Driven Catalysis

Carbon-nitride materials represent light-absorbing structures composed of earth-abundant elements capable of being leveraged for semiconductor photocatalysis at their surfaces. This study systematically investigates the addition of molecular modifiers to the synthesis of crystalline carbon nitrides to assess their effects on the materials’ structure, optical bandgap, and photocatalytic activity for hydrogen (H 2 ) and oxygen (O 2 ) evolution under ultraviolet and visible-light irradiation. Melamine and five pyrimidine-centered analogs were employed as building blocks to modify various heteroatoms within the polymeric framework. The modified materials were characterized with attention to the differences introduced by the monomeric modifiers and their influence on the resulting structures and compositions. The findings indicate that these changes significantly broaden the visible-light absorption range, albeit with the gradual loss of the bulk crystalline structure. As the loading of modifiers increased beyond 50%, a predominantly amorphous form of carbon nitride emerged. XPS, 13 C solid-state NMR, and SEM analyses corroborated the changes, which were attributed to modifications of the elemental composition and a reduced amount of Li cations and charge-balancing Cl anions owing to fewer binding sites in the intralayer cavities. In photocatalytic measurements under an ultraviolet 390 nm LED, and aided by photodeposited nanoparticle cocatalysts, the unmodified PTI-LiCl framework demonstrated the highest H 2 evolution rate (HER; 3.44 mmol·g –1 ·h –1 ) with an apparent quantum yield of 5.4%, along with total water splitting at rates of 163 μmol of H 2 ·g –1 ·h –1 and 75.6 μmol·O 2 g –1 ·h –1 . While PTI-LiCl showed trace activity under a visible-light 440 nm LED, all modified materials exhibited enhanced reactivity with as low as 5% molecular modifiers. The photocatalytic rates peaked at a 15% modification level when using 2,4,6-triaminopyrimidine, with rates of 33 μmol·g –1 ·h –1 for HER, along with 19.7 μmol of H 2 ·g –1 ·h –1 and 8.7 μmol of O 2 ·g –1 ·h –1 for total water splitting. Density functional theory calculations were used to probe electronic structure changes resulting from the modifications. Furthermore, these results elucidate the structural, optical, and electronic changes arising from the five selected molecular modifiers and their impact on the semiconductors’ photocatalytic properties.

Electrical conductivity↗

DOE OSTI2025

PhaseT3M: 3D imaging at 1.6 Å resolution via electron cryo-tomography with nonlinear phase retrieval

Electron cryo-tomography (cryo-ET) enables 3D imaging of complex, radiation-sensitive structures with molecular detail. However, image contrast from the interference of scattered electrons is nonlinear with atomic density and multiple scattering further complicates interpretation. These effects degrade resolution, particularly in conventional reconstruction algorithms, which assume linearity. Particle averaging can reduce such issues but is unsuitable for heterogeneous or dynamic samples ubiquitous in biology, chemistry, and materials sciences. Here, we develop a phase retrieval-based cryo-ET method, PhaseT3M. We experimentally demonstrate its application to an approximately 7 nm Co3O4 nanoparticle on an approximately 30 nm carbon substrate, achieving a maximum resolution of 1.6 Å, surpassing conventional limits using standard cryo-TEM equipment. PhaseT3M uses a multislice model for multiple scattering and Bayesian optimization for alignment and computational aberration correction, with a positivity constraint to recover ‘missing wedge’ information. Applied directly to biological particles, it enhances reconstruction quality and reduces artifacts, establishing a standard for routine 3D imaging with phase contrast.

Biophysics↗

DOE OSTI2024

Photoinduced Electron–Nuclear Dynamics of Fullerene and Its Monolayer Networks in Solvated Environments

The recently synthesized monolayer fullerene network in a quasi-hexagonal phase (qHP-C 60 ) exhibits superior electron mobility and optoelectronic properties compared to molecular fullerene (C 60 ), making it highly promising for a variety of applications. However, the microscopic carrier dynamics of qHP-C 60 remain unclear, particularly in realistic environments, which are of significant importance for applications in optoelectronic devices. Unfortunately, traditional ab initio methods are prohibitive for capturing the real-time carrier dynamics of such large systems due to their high computational cost. In this work, we present the first real-time electron–nuclear dynamics study of qHP-C 60 using velocity-gauge density functional tight binding, which enables us to perform several picoseconds of excited-state electron–nuclear dynamics simulations for nanoscale systems with periodic boundary conditions. When applied to C 60 , qHP-C 60 , and their solvated counterparts, we demonstrate that water/moisture significantly increases the electron–hole recombination time in C 60 but has little impact on qHP-C 60 . Our excited-state electron–nuclear dynamics calculations show that qHP-C 60 is extremely unique and enable exploration of time-resolved dynamics for understanding excited-state processes of large systems in complex, solvated environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Role of Metal Cocatalysts in the Photocatalytic Production of Hydrogen from Water Revisited

The use of photocatalysts to promote the production of molecular hydrogen from water, following the so-called water splitting reaction, continues to be a promising route for the green production of fuels. The molecular basis of this photocatalysis is the photoexcitation of electrons from the valence band of semiconductors to their conduction band, from which they can be transferred to chemical reactants, protons in the case of water, to promote a reduction reaction. The mechanism by which such a process takes place has been studied extensively using titanium oxide, a simple material that fulfills most requirements for water splitting. However, photocatalysis with TiO 2 tends to be highly inefficient; a cocatalyst, commonly a late transition metal (Au, Pt) in nanoparticle form, needs to be added to facilitate the production of H 2 . The metal is widely believed to help with the scavenging of the excited electrons from the conduction band of the semiconductor in order to prevent their recombination with the accompanying hole formed in the valence band, a step that cancels the initial photon absorption and competes with the photolytic chemical reduction. Here we review and analyze the molecular basis for that mechanism and argue for an alternative explanation, that the role of the metal is to help with the recombination of the atomic hydrogen atoms produced by proton reduction on the semiconductor surface instead. First, we summarize what is known about the electronic structure of these photocatalysts and how the electronic levels need to line up for the reduction of protons in water to be feasible. Next, we review the current understanding of the dynamics of the steps associated with the absorption of photons, the de-excitation via electron–hole pair recombination and fluorescence decay, and the electronic transitions that lead to proton reduction, and contrast those with the rates of the chemical steps required to produce molecular hydrogen. The following section addresses the changes introduced by the addition of the metal cocatalyst, comparatively evaluating its role as either an electron scavenger or a promoter of the recombination of hydrogen atoms. A discussion of the viable chemical mechanisms for the latter pathway is included. Finally, we briefly mention other associated aspects of this photocatalysis, including the possible promotion of H 2 production with visible light via resonant excitation of the surface plasmon of Au nanoparticles, the use of single-metal (Au, Pt) atom catalysts and of yolk–shell nanostructures, and the reduction of organic molecules. We end with a brief personal perspective on the possible generality of the concepts introduced in this Critical Review.

08 HYDROGEN↗

DOE OSTI2025

Light control of intramolecular nuclear dynamics by vortex electron localization

In strong-field ionization of molecules, intense light pulses are thought to have a negligible direct influence on atomic nuclei. Molecular dissociation is thus expected to be determined by the geometrical configuration of the molecular ion at the ionization instant. Contrary to this picture, we observe a counterintuitive electron-proton angular correlation and the formation of proton vortices following strong-field ionization of H 2 molecules by bicircularly polarized two-color laser fields. We explain this phenomenon by the pathway interference and localization of the residual H 2 ⁡+ electron in different angular-momentum states formed in the tail of the driving laser pulse. We validate this interpretation by combining a quantum-mechanical numerical simulation of the field-driven coupled electronic-nuclear dynamics and a semiclassical-trajectory model for the phase accumulation of the laser-driven electronic-nuclear wave packet. Our joint experimental and theoretical study reveals a general picture of vortex electron localization which can be used for controlling molecular-bond breaking with circularly polarized laser fields.

Atomic & molecular processes in external fields↗

DOE OSTI2024

Exploring the exact limits of the real-time equation-of-motion coupled cluster cumulant Green’s functions

In this paper, we analyze the properties of the recently proposed real-time equation-of-motion coupled-cluster (RT-EOM-CC) cumulant Green’s function approach [Rehr et al., J. Chem. Phys. 152, 174113 (2020)]. We specifically focus on identifying the limitations of the original time-dependent coupled cluster (TDCC) ansatz and propose an enhanced double TDCC ansatz, ensuring the exactness in the expansion limit. In addition, we introduce a practical cluster-analysis-based approach for characterizing the peaks in the computed spectral function from the RT-EOM-CC cumulant Green’s function approach, which is particularly useful for the assignments of satellite peaks when many-body effects dominate the spectra. Our preliminary numerical tests focus on reproducing, approximating, and characterizing the exact impurity Green’s function of the three-site and four-site single impurity Anderson models using the RT-EOM-CC cumulant Green’s function approach. The numerical tests allow us to have a direct comparison between the RT-EOM-CC cumulant Green’s function approach and other Green’s function approaches in the numerical exact limit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Consistent and reproducible computation of the glass transition temperature from molecular dynamics simulations

In many fields, from semiconductors for opto-electronic applications to ionic liquids (ILs) for separations, the glass transition temperature (Tg) of a material is a useful gauge for its potential use in practical settings. As a result, there is a great deal of interest in predicting Tg using molecular simulations. However, the uncertainty and variation in the trend shift method, a common approach in simulations to predict Tg, can be high. This is due to the need for human intervention in defining a fitting range for linear fits of density with temperature assumed for the liquid and glass phases across the simulated cooling. The definition of such fitting ranges then defines the estimate for the Tg as the intersection of linear fits. We eliminate this need for human intervention by leveraging the Shapiro–Wilk normality test and proposing an algorithm to define the fitting ranges and, consequently, Tg. Through this integration, we incorporate into our automated methodology that residuals must be normally distributed around zero for any fit, a requirement that must be met for any regression problem. Consequently, fitting ranges for realizing linear fits for each phase are statistically defined rather than visually inferred, obtaining an estimate for Tg without any human intervention. The method is also capable of finding multiple linear regimes across density vs temperature curves. We compare the predictions of our proposed method across multiple IL and semiconductor molecular dynamics simulation results from the literature and compare other proposed methods for automatically detecting Tg from density–temperature data. We believe that our proposed method would allow for more consistent predictions of Tg. We make this methodology available and open source through GitHub.

Chemistry↗

DOE OSTI2026

Cryogenic electron tomography by the numbers: Charting underexplored lineages in structural cell biology

Imaging cells and their interactions across the whole biosphere with molecular-scale resolution is key for understanding structure–function relations. Cryogenic electron tomography (cryo-ET) is a powerful method for obtaining this critical information. However, cryo-ET studies are challenging and often limited to a small number of cell types per study. Here, we collate cryo-ET data from hundreds of cells and tissues across the biosphere to i) identify emerging methodological trends, ii) pinpoint strategies to reduce imaging time and costs, iii) quantitatively compare methods for cell freezing and sectioning, and iv) census cryo-ET species coverage across all domains of life. Comparing the fraction of cellular material within a single lamella across all domains of life reveals an order of magnitude difference between eukaryotes (1%) compared to bacteria (9%) and archaea (14%). We calculate the fraction of cellular material which can be imaged using distinct sectioning methods on multicellular communities and tissues—identifying serial lift-out as a powerful approach for obtaining more complete cellular depictions. Finally, we show that the biodiversity of current cryo-ET studies is 2 to 3 orders of magnitude lower than in sequence libraries and 4 to 5 lower than the total predicted on Earth. Our analyses reveal major evolutionary lineages which remain critically understudied and highlight where future cryo-ET research would be most impactful.

HPF↗

DOE OSTI2024

Distinct vibrational motions promote disparate excited-state decay pathways in cofacial perylenediimide dimers

A complex interplay of structural, electronic, and vibrational degrees of freedom underpins the fate of molecular excited states. Organic assemblies exhibit a myriad of excited-state decay processes, such as symmetry-breaking charge separation (SB-CS), excimer (EX) formation, singlet fission, and energy transfer. Recent studies of cofacial and slip-stacked perylene-3,4:9,10-bis(dicarboximide) (PDI) multimers demonstrate that slight variations in core substituents and H- or J-type aggregation can determine whether the system follows an SB-CS pathway or an EX one. However, questions regarding the relative importance of structural properties and molecular vibrations in driving the excited-state dynamics remain. Here, we use a combination of two-dimensional electronic spectroscopy, femtosecond stimulated Raman spectroscopy, and quantum chemistry computations to compare the photophysics of two PDI dimers. The dimer with 1,7-bis(pyrrolidin-1′-yl) substituents (5PDI2) undergoes ultrafast SB-CS from a photoexcited mixed state, while the dimer with bis-1,7-(3′,5′-di-t-butylphenoxy) substituents (PPDI2) rapidly forms an EX state. Examination of their quantum beating features reveals that SB-CS in 5PDI2 is driven by the collective vibronic coupling of two or more excited-state vibrations. In contrast, we observe signatures of low-frequency vibrational coherence transfer during EX formation by PPDI2, which aligns with several previous studies. We conclude that key electronic and structural differences between 5PDI2 and PPDI2 determine their markedly different photophysics.

Chemistry↗

DOE OSTI2025

A high-resolution molecular spin-photon interface at telecommunication wavelengths

Optically addressable electronic spins in polyatomic molecules are a promising platform for quantum information science, with the potential to enable scalable qubit design and integration through atomistic tunability and nanoscale localization. However, optical state- and site-selection are an open challenge. Here, in this work, we introduce an organo-erbium spin qubit in which narrow (megahertz-scale) optical and spin transitions couple to provide high-resolution access to spin degrees of freedom with telecommunication-frequency light. This spin-photon interface enables demonstration of optical spin polarization and readout that distinguishes between spin states and magnetically inequivalent sites in a molecular crystal. Operation at frequencies compatible with mature photonic and microwave devices provides an opportunity for engineering scalable, integrated molecular spin-optical quantum technologies.

Weiss, Leah R. [University of Chicago, IL (United ↗

DOE OSTI2024

From Coherence to Function: Exploring the Connection in Chemical Systems

The role of quantum mechanical coherences or coherent superposition states in excited state processes has received considerable attention in the last two decades largely due to advancements in ultrafast laser spectroscopy. These coherence effects hold promise for enhancing the efficiency and robustness of functionally relevant processes, even when confronted with energy disorder and environmental fluctuations. Understanding coherence deeply drives us to unravel mechanisms and dynamics controlled by order and synchronization at a quantum mechanical level, envisioning optical control of coherence to enhance functions or create new ones in molecular and material systems. In this frontier, the interplay between electronic and vibrational dynamics, specifically the influence of vibrations in directing electronic dynamics, has emerged as the leading principle. Here, two energetically disparate quantum degrees of freedom work in-sync to dictate the trajectory of an excited state reaction. Moreover, with the vibrational degree being directly related to the structural composition of molecular or material systems, new molecular designs could be inspired by tailoring certain structural elements. In the realm of chemical kinetics, our understanding of the dynamics of chemical transformations is underpinned by fundamental theories, such as transition state theory, activated rate theory, and Marcus theory. These theories elucidate reaction rates by considering the energy barriers that must be overcome for reactants to transform into products. Those barriers are surmounted by the stochastic nature of energy gap fluctuations within reacting systems, emphasizing that the reaction coordinate, the pathway from reactants to products, is not rigidly defined by a specific vibrational motion but encompasses a diverse array of molecular motions. While less is known about the involvement of specific intramolecular vibrational modes, their significance in certain cases cannot be overlooked. In this Account, we summarize key experimental findings that offer deeper insights into the complex electronic–vibrational trajectories encompassing excited states afforded from state-of-the-art ultrafast laser spectroscopy in three exemplary processes: photoinduced electron transfer, singlet–triplet intersystem crossing, and intramolecular vibrational energy flow in molecular systems. We delve into the rapid decoherence, or loss of phase and amplitude correlations, of vibrational coherences along promoter vibrations during subpicosecond intersystem crossing dynamics in a series of binuclear platinum complexes. This rapid decoherence illustrates the vibration-driven reactive pathways from the Franck–Condon state to the curve crossing region. We also explore the generation of new vibrational coherences induced by impulsive reaction dynamics rather than by the laser pulse in these systems, which sheds light on specific energy dissipation pathways and thereby on the progression of the reaction trajectory in the vicinity of the curve crossing on the product side. Another property of vibrational coherences, amplitude, reveals how energy can flow from one vibration to another in the electronic excited state of a terpyridine–molybdenum complex hosting a nonreactive dinitrogen substrate. In conclusion, a slight change in vibrational energy triggers a quasi-resonant interaction, leading to constructive wavepacket interference and ultimately intramolecular vibrational redistribution from a Franck–Condon active terpyridine vibration to a dinitrogen stretching vibration, energizing the dinitrogen bond.

Electrical energy↗

DOE OSTI2025

Chlorine gas and anion radical reactivity in molten salts and the link to chlorobasicity

Next-generation nuclear power plants may include exciting novel designs in which molten salts are the coolant or a combination of the coolant and fuel. Whereas it is straightforward to see why having a low volatility coolant can be advantageous for safety, much is not understood about the production of volatile halogen gases as a result of radiation and even less is known about the distribution of these species at and away from interfaces. Using first principles molecular dynamics simulations, we investigate the product of the disproportionation reaction between chlorine anion radicals (nominally Cl 2 ˙ − ) in the bulk and slab configurations. We find that the product depends on the chlorobasicity of the medium. For example, in ZnCl 2 , Cl 2 forms, but in a eutectic mixture of LiCl and KCl, Cl 3 − is formed as a product. We also find that Cl 3 − prefers to form at the vapor interface and this may have implications for corrosion and reactivity. Furthermore, the mechanisms of the mobility of Cl 2 and Cl 3 − are radically different, the first one being vehicular and the second Grotthus-like. Chlorobasicity is linked to the electronic structure of the host melt; ZnCl 2 forms extended networks along which metal ions and anionic counterions have significant electronic orbital overlap forming long, linear, molecular-like constructs; the opposite is true for the alkali metal eutectic salt.

Nguyen, Hung H. [Univ. of Iowa, Iowa City, IA (Uni↗

DOE OSTI2024

Secondary structure determines electron transport in peptides

Proteins play a key role in biological electron transport, but the structure–function relationships governing the electronic properties of peptides are not fully understood. Despite recent progress, understanding the link between peptide conformational flexibility, hierarchical structures, and electron transport pathways has been challenging. Here, we use single-molecule experiments, molecular dynamics (MD) simulations, nonequilibrium Green’s function-density functional theory (NEGF-DFT), and unsupervised machine learning to understand the role of secondary structure on electron transport in peptides. Our results reveal a two-state molecular conductance behavior for peptides across several different amino acid sequences. MD simulations and Gaussian mixture modeling are used to show that this two-state molecular conductance behavior arises due to the conformational flexibility of peptide backbones, with a high-conductance state arising due to a more defined secondary structure (beta turn or 3 10 helices) and a low-conductance state occurring for extended peptide structures. These results highlight the importance of helical conformations on electron transport in peptides. Conformer selection for the peptide structures is rationalized using principal component analysis of intramolecular hydrogen bonding distances along peptide backbones. Molecular conformations from MD simulations are used to model charge transport in NEGF-DFT calculations, and the results are in reasonable qualitative agreement with experiments. Projected density of states calculations and molecular orbital visualizations are further used to understand the role of amino acid side chains on transport. Overall, our results show that secondary structure plays a key role in electron transport in peptides, which provides broad avenues for understanding the electronic properties of proteins.

Science & Technology - Other Topics↗

DOE OSTI2025

Large Hyperfine Coupling Arising from Pseudo- 2 S Ground States in a Series of Lutetium(II) Metallocene Complexes

The synthesis of molecules with strong coupling between electronic and nuclear spins represents an important challenge in molecular quantum information science. Here, we report the synthesis and characterization of the divalent lutetium metallocene complexes Lu(Cp Me 5 )(Cp iPr 5 ) (Cp Me 5 = pentamethylcyclopentadienyl; Cp iPr 5 = pentaisopropylcyclopentadienyl), Lu(Cp iPr 4 Et ) 2 (Cp iPr 4 Et = ethyltetraisopropylcyclopentadienyl), and Lu(Cp iPr 4 ) 2 (Cp iPr 4 = tetraisopropylcyclopentadienyl). The molecular structures of these complexes, as determined through singlecrystal X-ray diffraction, feature a common bent sandwich geometry, with average Cp–Lu–Cp angles ranging from 159.9° to 152.6°. Analysis of continuous-wave electron paramagnetic resonance (EPR) spectra for the complexes reveals nearly isotropic g tensors with only a slight deviation from that of a free electron. Moreover, an extremely large splitting of the eight-line spectra indicates the presence of strong hyperfine coupling, and simulations provide isotropic hyperfine coupling constants of A iso = 4.38, 4.30, and 4.17 GHz across the series, where the value of A iso is found to decrease as the Cp–Lu–Cp angle becomes more acute. Notably, these values are the largest yet observed for any lanthanide complex. Moreover, EPR and computational analysis show that the large values of A iso stem from large s-orbital character up to 41.2% in the corresponding singly occupied molecular orbitals. To our knowledge, this degree of s-character in a molecular orbital is the largest yet reported for an open-shell isolable complex. These results outline a general strategy toward the isolation of paramagnetic molecules with strong hyperfine coupling and highly isotropic doublet electronic ground states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗