Ligand field design enables quantum manipulation of spins in Ni2+ complexes.

Creating the next generation of quantum systems requires control and tunability, which are key features of molecules. To design these systems, one must consider the ground-state and excited-state manifolds. One class of systems with promise for quantum sensing applications, which require water solubility, are d8 Ni2+ ions in octahedral symmetry. Yet, most Ni2+ complexes feature large zero-field splitting, precluding manipulation by commercial microwave sources due to the relatively large spin-orbit coupling constant of Ni2+ (630 cm-1). Since low lying excited states also influence axial zero-field splitting, D, a combination of strong field ligands and rigidly held octahedral symmetry can ameliorate these challenges. Towards these ends, we performed a theoretical and computational analysis of the electronic and magnetic structure of a molecular qubit, focusing on the impact of ligand field strength on D. Based on those results, we synthesized 1, [Ni(ttcn)2](BF4)2 (ttcn = 1,4,7-trithiacyclononane), which we computationally predict will have a small D (Dcalc = +1.15 cm-1). High-field high-frequency electron paramagnetic resonance (EPR) data yield spin Hamiltonian parameters: gx = 2.1018(15), gx = 2.1079(15), gx = 2.0964(14), D = +0.555(8) cm-1 and E = +0.072(5) cm-1, which confirm the expected weak zero-field splitting. Dilution of 1 in the diamagnetic Zn analogue, [Ni0.01Zn0.99(ttcn)2](BF4)2 (1') led to a slight increase in D to ∼0.9 cm-1. The design criteria in minimizing D in 1via combined computational and experimental methods demonstrates a path forward for EPR and optical addressability of a general class of S = 1 spins.

Evaluation of the New England Office Based Addiction Treatment ECHO: A Tool for Strengthening the Addiction Workforce.

INTRODUCTION: Reducing substance-related morbidity requires an educated and well-supported workforce. The New England Office Based Addiction Treatment Extension for Community Healthcare Outcomes (NE OBAT ECHO) began in 2019 to support community-based addiction care teams through virtual mentoring and case-based learning. We sought to characterize the program's impact on the knowledge and attitudes of NE OBAT ECHO participants. METHODS: We conducted an 18-month prospective evaluation of the NE OBAT ECHO. Participants registered for 1 of 2 successive ECHO clinics. Each 5-month clinic included ten 1.5-hour sessions involving brief didactic lectures and de-identified patient case presentations. Participants completed surveys at Month-0, -6, -12, and -18 to assess attitudes about working with patients who use drugs and evidence based practices (EBPs), stigma toward people who use drugs, and addiction treatment knowledge. We compared outcomes using 2 approaches: (i) between-groups, which involved comparing the first intervention group to the delayed intervention (comparison) group, and (ii) within-groups, which involved comparing outcomes at different time points for all participants. In the within-group approach, each participant acted as their own control. RESULTS: Seventy-six health professionals participated in the NE OBAT ECHO, representing various roles in addiction care teams. Approximately half (47% [36/76]) practiced primary care, internal, or family medicine. The first intervention group reported improved job satisfaction and openness toward EBPs compared to the delayed intervention group. Within-group analyses revealed that ECHO participation was associated with increased positive perceptions of role adequacy, support, legitimacy, and satisfaction 6 months following program completion. No changes were identified in willingness to adopt EBPs or treatment knowledge. Stigma toward people who use drugs was persistent in both groups across time points. CONCLUSIONS: NE OBAT ECHO may have improved participants' confidence and satisfaction providing addiction care. ECHO is likely an effective educational tool for expanding the capacity of the addiction workforce.

Targeting the PAI-1 Mechanism with a Small Peptide Increases the Efficacy of Alteplase in a Rabbit Model of Chronic Empyema.

The incidence of empyema is increasing and associated with a mortality rate of 20% in patients older than 65 years. Since 30% of patients with advanced empyema have contraindications to surgical treatment, novel, low-dose, pharmacological treatments are needed. A Streptococcus pneumoniae-induced rabbit model of chronic empyema recapitulates the progression, loculation, fibrotic repair, and pleural thickening of human disease. Treatment with single chain (sc) urokinase (scuPA) or tissue type (sctPA) plasminogen activators in doses 1.0-4.0 mg/kg were only partially effective in this model. Docking Site Peptide (DSP; 8.0 mg/kg), which decreased the dose of sctPA for successful fibrinolytic therapy in acute empyema model did not improve efficacy in combination with 2.0 mg/kg scuPA or sctPA. However, a two-fold increase in either sctPA or DSP (4.0 and 8.0 mg/kg or 2.0 and 16.0 mg/kg sctPA and DSP, respectively) resulted in 100% effective outcome. Thus, DSP-based Plasminogen Activator Inhibitor 1-Targeted Fibrinolytic Therapy (PAI-1-TFT) of chronic infectious pleural injury in rabbits increases the efficacy of alteplase rendering ineffective doses of sctPA effective. PAI-1-TFT represents a novel, well-tolerated treatment of empyema that is amenable to clinical introduction. The chronic empyema model recapitulates increased resistance of advanced human empyema to fibrinolytic therapy, thus allowing for studies of muti-injection treatments.

Electronic Spin Qubit Candidates Arrayed within Layered Two-Dimensional Polymers.

Molecular electronic spin qubits are promising candidates for quantum information science applications because they can be reliably produced and engineered via chemical design. Embedding electronic spin qubits within two-dimensional polymers (2DPs) offers the possibility to systematically engineer inter-qubit interactions while maintaining long coherence times, both of which are prerequisites to their technological utility. Here, we introduce electronic spin qubits into a diamagnetic 2DP by n-doping naphthalene diimide subunits with varying amounts of CoCp2 and analyze their spin densities by quantitative electronic paramagnetic resonance spectroscopy. Low spin densities (e.g., 6.0 × 1012 spins mm-3) enable lengthy spin-lattice (T1) and spin-spin relaxation (T2) times across a range of temperatures, ranging from T1 values of 164 ms at 10 K to 30.2 µs at 296 K and T2 values of 2.36 µs at 10 K to 0.49 µs at 296 K for the lowest spin density sample examined. Higher spin densities and temperatures were both found to diminish T1 times, which we attribute to detrimental cross-relaxation from spin-spin dipolar interactions and spin-phonon coupling, respectively. Higher spin densities decreased T2 times and modulated the T2 temperature dependence. We attribute these differences to the competition between hyperfine and dipolar interactions for electron spin decoherence, with the dominant interaction transitioning from the former to the latter as spin density and temperature increase. Overall, this investigation demonstrates that dispersing electronic spin qubits within layered 2DPs enables chemical control of their inter-qubit interactions and spin decoherence times.

Could the Quantum Internet Be Comprised of Molecular Spins with Tunable Optical Interfaces?

One goal of the second quantum revolution is developing an approach to transmit coherent quantum information across the world, forming the basis of the quantum Internet. Achieving this lofty goal will require scalable and tunable materials that allow for cross-platform interconnections. Solution-processable molecular systems designed from the ground up are poised to introduce the necessary tunability to meet these needs. In this Perspective, we describe the components of a quantum network, outline the criteria to create molecular systems suitable for networking applications, and discuss the pathway to generate spin-photon entanglement, a first step toward remote entanglement between molecular spins in a network. We also describe some initial steps to optimize molecular spins for potential integration into quantum networks as readily deployable qubits in network nodes. Throughout this Perspective, we highlight the tremendous potential of molecular systems for the quantum Internet and illustrate openings for chemists in this nascent field.

Chemical control of spin-lattice relaxation to discover a room temperature molecular qubit.

The second quantum revolution harnesses exquisite quantum control for a slate of diverse applications including sensing, communication, and computation. Of the many candidates for building quantum systems, molecules offer both tunability and specificity, but the principles to enable high temperature operation are not well established. Spin-lattice relaxation, represented by the time constant T 1, is the primary factor dictating the high temperature performance of quantum bits (qubits), and serves as the upper limit on qubit coherence times (T 2). For molecular qubits at elevated temperatures (>100 K), molecular vibrations facilitate rapid spin-lattice relaxation which limits T 2 to well below operational minimums for certain quantum technologies. Here we identify the effects of controlling orbital angular momentum through metal coordination geometry and ligand rigidity via π-conjugation on T 1 relaxation in three four-coordinate Cu2+ S = ½ qubit candidates: bis(N,N'-dimethyl-4-amino-3-penten-2-imine) copper(ii) (Me2Nac)2 (1), bis(acetylacetone)ethylenediamine copper(ii) Cu(acacen) (2), and tetramethyltetraazaannulene copper(ii) Cu(tmtaa) (3). We obtain significant T 1 improvement upon changing from tetrahedral to square planar geometries through changes in orbital angular momentum. T 1 is further improved with greater π-conjugation in the ligand framework. Our electronic structure calculations reveal that the reduced motion of low energy vibrations in the primary coordination sphere slows relaxation and increases T 1. These principles enable us to report a new molecular qubit candidate with room temperature T 2 = 0.43 µs, and establishes guidelines for designing novel qubit candidates operating above 100 K.

Synthesis of the Candidate Topological Compound Ni3Pb2.

Spin-orbit coupling enables the realization of topologically nontrivial ground states. As spin-orbit coupling increases with increasing atomic number, compounds featuring heavy elements, such as lead, offer a pathway toward creating new topologically nontrivial materials. By employing a high-pressure flux synthesis method, we synthesized single crystals of Ni3Pb2, the first structurally characterized bulk binary phase in the Ni-Pb system. Combining experimental and theoretical techniques, we examined structure and bonding in Ni3Pb2, revealing the impact of chemical substitutions on electronic structure features of importance for controlling topological behavior. From these results, we determined that Ni3Pb2 completes a series of structurally related transition-metal-heavy main group intermetallic materials that exhibit diverse electronic structures, opening a platform for synthetically tunable topologically nontrivial materials.

Controlled n-Doping of Naphthalene-Diimide-Based 2D Polymers.

2D polymers (2DPs) are promising as structurally well-defined, permanently porous, organic semiconductors. However, 2DPs are nearly always isolated as closed shell organic species with limited charge carriers, which leads to low bulk conductivities. Here, the bulk conductivity of two naphthalene diimide (NDI)-containing 2DP semiconductors is enhanced by controllably n-doping the NDI units using cobaltocene (CoCp2 ). Optical and transient microwave spectroscopy reveal that both as-prepared NDI-containing 2DPs are semiconducting with sub-2 eV optical bandgaps and photoexcited charge-carrier lifetimes of tens of nanoseconds. Following reduction with CoCp2 , both 2DPs largely retain their periodic structures and exhibit optical and electron-spin resonance spectroscopic features consistent with the presence of NDI-radical anions. While the native NDI-based 2DPs are electronically insulating, maximum bulk conductivities of >10-4  S cm-1 are achieved by substoichiometric levels of n-doping. Density functional theory calculations show that the strongest electronic couplings in these 2DPs exist in the out-of-plane (π-stacking) crystallographic directions, which indicates that cross-plane electronic transport through NDI stacks is primarily responsible for the observed electronic conductivity. Taken together, the controlled molecular doping is a useful approach to access structurally well-defined, paramagnetic, 2DP n-type semiconductors with measurable bulk electronic conductivities of interest for electronic or spintronic devices.

Tunable Cr4+ Molecular Color Centers.

The inherent atomistic precision of synthetic chemistry enables bottom-up structural control over quantum bits, or qubits, for quantum technologies. Tuning paramagnetic molecular qubits that feature optical-spin initialization and readout is a crucial step toward designing bespoke qubits for applications in quantum sensing, networking, and computing. Here, we demonstrate that the electronic structure that enables optical-spin initialization and readout for S = 1, Cr(aryl)4, where aryl = 2,4-dimethylphenyl (1), o-tolyl (2), and 2,3-dimethylphenyl (3), is readily translated into Cr(alkyl)4 compounds, where alkyl = 2,2,2-triphenylethyl (4), (trimethylsilyl)methyl (5), and cyclohexyl (6). The small ground state zero field splitting values (<5 GHz) for 1-6 allowed for coherent spin manipulation at X-band microwave frequency, enabling temperature-, concentration-, and orientation-dependent investigations of the spin dynamics. Electronic absorption and emission spectroscopy confirmed the desired electronic structures for 4-6, which exhibit photoluminescence from 897 to 923 nm, while theoretical calculations elucidated the varied bonding interactions of the aryl and alkyl Cr4+ compounds. The combined experimental and theoretical comparison of Cr(aryl)4 and Cr(alkyl)4 systems illustrates the impact of the ligand field on both the ground state spin structure and excited state manifold, laying the groundwork for the design of structurally precise optically addressable molecular qubits.

A Molecular Approach to Quantum Sensing.

The second quantum revolution hinges on the creation of materials that unite atomic structural precision with electronic and structural tunability. A molecular approach to quantum information science (QIS) promises to enable the bottom-up creation of quantum systems. Within the broad reach of QIS, which spans fields ranging from quantum computation to quantum communication, we will focus on quantum sensing. Quantum sensing harnesses quantum control to interrogate the world around us. A broadly applicable class of quantum sensors would feature adaptable environmental compatibility, control over distance from the target analyte, and a tunable energy range of interaction. Molecules enable customizable "designer" quantum sensors with tunable functionality and compatibility across a range of environments. These capabilities offer the potential to bring unmatched sensitivity and spatial resolution to address a wide range of sensing tasks from the characterization of dynamic biological processes to the detection of emergent phenomena in condensed matter. In this Outlook, we outline the concepts and design criteria central to quantum sensors and look toward the next generation of designer quantum sensors based on new classes of molecular sensors.

Spectral Addressability in a Modular Two Qubit System.

The combination of structural precision and reproducibility of synthetic chemistry is perfectly suited for the creation of chemical qubits, the core units of a quantum information science (QIS) system. By exploiting the atomistic control inherent to synthetic chemistry, we address a fundamental question of how the spin-spin distance between two qubits impacts electronic spin coherence. To achieve this goal, we designed a series of molecules featuring two spectrally distinct qubits, an early transition metal, Ti3+, and a late transition metal, Cu2+ with increasing separation between the two metals. Crucially, we also synthesized the monometallic congeners to serve as controls. The spectral separation between the two metals enables us to probe each metal individually in the bimetallic species and compare it with the monometallic control samples. Across a range of 1.2-2.5 nm, we find that electron spins have a negligible effect on coherence times, a finding we attribute to the distinct resonance frequencies. Coherence times are governed, instead, by the distance to nuclear spins on the other qubit's ligand framework. This finding offers guidance for the design of spectrally addressable molecular qubits.

Computationally Directed Discovery of MoBi2.

Incorporating bismuth, the heaviest element stable to radioactive decay, into new materials enables the creation of emergent properties such as permanent magnetism, superconductivity, and nontrivial topology. Understanding the factors that drive Bi reactivity is critical for the realization of these properties. Using pressure as a tunable synthetic vector, we can access unexplored regions of phase space to foster reactivity between elements that do not react under ambient conditions. Furthermore, combining computational and experimental methods for materials discovery at high-pressures provides broader insight into the thermodynamic landscape than can be achieved through experiment alone, informing our understanding of the dominant chemical factors governing structure formation. Herein, we report our combined computational and experimental exploration of the Mo-Bi system, for which no binary intermetallic structures were previously known. Using the ab initio random structure searching (AIRSS) approach, we identified multiple synthetic targets between 0-50 GPa. High-pressure in situ powder X-ray diffraction experiments performed in diamond anvil cells confirmed that Mo-Bi mixtures exhibit rich chemistry upon the application of pressure, including experimental realization of the computationally predicted CuAl2-type MoBi2 structure at 35.8(5) GPa. Electronic structure and phonon dispersion calculations on MoBi2 revealed a correlation between valence electron count and bonding in high-pressure transition metal-Bi structures as well as identified two dynamically stable ambient pressure polymorphs. Our study demonstrates the power of the combined computational-experimental approach in capturing high-pressure reactivity for efficient materials discovery.

Fast and programmable locomotion of hydrogel-metal hybrids under light and magnetic fields.

The design of soft matter in which internal fuels or an external energy input can generate locomotion and shape transformations observed in living organisms is a key challenge. Such materials could assist in productive functions that may range from robotics to smart management of chemical reactions and communication with cells. In this context, hydrated matter that can function in aqueous media would be of great interest. Here, we report the design of hydrogels containing a scaffold of high-aspect ratio ferromagnetic nanowires with nematic order dispersed in a polymer network that change shape in response to light and experience torques in rotating magnetic fields. The synergistic response enables fast walking motion of macroscopic objects in water on either flat or inclined surfaces and also guides delivery of cargo through rolling motion and light-driven shape changes. The theoretical description of the response to the external energy input allowed us to program specific trajectories of hydrogel objects that were verified experimentally.

Trigonal Bipyramidal V3+ Complex as an Optically Addressable Molecular Qubit Candidate.

Synthetic chemistry enables a bottom-up approach to quantum information science, where atoms can be deterministically positioned in a quantum bit or qubit. Two key requirements to realize quantum technologies are qubit initialization and read-out. By imbuing molecular spins with optical initialization and readout mechanisms, analogous to solid-state defects, molecules could be integrated into existing quantum infrastructure. To mimic the electronic structure of optically addressable defect sites, we designed the spin-triplet, V3+ complex, (C6F5)3trenVCNtBu (1). We measured the static spin properties as well as the spin coherence time of 1 demonstrating coherent control of this spin qubit with a 240 GHz electron paramagnetic resonance spectrometer powered by a free electron laser. We found that 1 exhibited narrow, near-infrared photoluminescence (PL) from a spin-singlet excited state. Using variable magnetic field PL spectroscopy, we resolved emission into each of the ground-state spin sublevels, a crucial component for spin-selective optical initialization and readout. This work demonstrates that trigonally symmetric, heteroleptic V3+ complexes are candidates for optical spin addressability.

Pressure-Induced Collapse of Magnetic Order in Jarosite.

We report a pressure-induced phase transition in the frustrated kagomé material jarosite at ∼45 GPa, which leads to the disappearance of magnetic order. Using a suite of experimental techniques, we characterize the structural, electronic, and magnetic changes in jarosite through this phase transition. Synchrotron powder x-ray diffraction and Fourier transform infrared spectroscopy experiments, analyzed in aggregate with the results from density functional theory calculations, indicate that the material changes from a R3[over ¯]m structure to a structure with a R3[over ¯]c space group. The resulting phase features a rare twisted kagomé lattice in which the integrity of the equilateral Fe^{3+} triangles persists. Based on symmetry arguments we hypothesize that the resulting structural changes alter the magnetic interactions to favor a possible quantum paramagnetic phase at high pressure.

Nickel(II) Metal Complexes as Optically Addressable Qubit Candidates.

The inherent atomic level structural control of synthetic chemistry enables the creation of qubits, the base units of a quantum information science system, designed for a target application. For quantum sensing applications, enabling optical read-out of spin in tunable molecular systems, akin to defect-based systems, would be transformative. This approach would bring together molecular tunability with optical read-out technology. In theory, nickel ions in octahedral symmetry meet all the criteria for optical readout of spin. Yet, to the best of our knowledge, there are no pulse EPR studies on Ni2+ molecules. We identified two compounds featuring highly symmetric Ni2+ centers, thereby engendering weak zero-field splitting to enable EPR addressability: [Ni(phen)3](BF4)2 (1) and [Ni(pyr3)2](BF4)2 (2) (phen = 1,10-phenanthroline; pyr3 = tris-2-pyridyl-methane). Crucially, these complexes feature the requisite strong field ligands to enable emission for optical addressability. We extracted axial zero-field splitting parameters of D = +0.9 cm-1 and +2.7 cm-1 for 1 and 2, respectively, enabling pulse EPR measurements. Both compounds produce emission at λmax = 938-944 nm. The aggregate of these results expands the catalogue of qubit materials to Ni2+-based compounds and offers a future pathway for optical readout of these molecules.

Control of the Porosity in Manganese Trimer-Based Metal-Organic Frameworks by Linker Functionalization.

Manganese complexes have attracted significant interest in chemical industries and academic research for their application as catalysts owing to their ability to attain a variety of oxidation states. Generally, sterically bulky ligands are required to isolate molecular homogeneous catalysts in order to prevent decomposition. Herein, we capitalize on the catalytic properties of Mn and circumvent the instability of these complexes through incorporation of Mn-atoms into porous crystalline frameworks, such as metal-organic frameworks (MOFs). MOFs are able to enhance the stability of these catalysts while also providing accessibility to the Mn sites for enhanced reactivity. We solvothermally synthesized two trinuclear Mn-based MOFs, namely [Mn3O(BDC)3(H2O)3]n (Mn-MIL-88, where H2BDC = benzene-1,4-dicarboxylic acid) and [Mn3O(BDC-Me4)3(H2O)3]n (Mn-MIL-88-Me4, where H2BDC-Me4 = 2,3,5,6-tetramethylterephthalic acid). Through comprehensive single-crystal X-ray diffraction, spectroscopic, and magnetic studies, we revealed that both MOFs are in a Mn(II/III) mixed-valence state instead of the commonly observed Mn(III) oxidation state. Furthermore, the use of a methylated linker (BDC-Me4) allowed access to permanent porosity in Mn-MIL-88-Me4, which is an analogue of the flexible MIL-88 family, yielding a catalyst for alcohol oxidation.

Synthetic investigation of competing magnetic interactions in 2D metal-chloranilate radical frameworks.

The discovery of emergent materials lies at the intersection of chemistry and condensed matter physics. Synthetic chemistry offers a pathway to create materials with the desired physical and electronic structures that support fundamentally new properties. Metal-organic frameworks are a promising platform for bottom-up chemical design of new materials, owing to their inherent chemical predictability and tunability relative to traditional solid-state materials. Herein, we describe the synthesis and magnetic characterization of a new 2,5-dihydroxy-1,4-benzoquinone based material, (NMe2H2)3.5Ga2(C6O4Cl2)3 (1), which features radical-based electronic spins on the sites of a kagomé lattice, a geometric lattice known to engender exotic electronic properties. Vibrational and electronic spectroscopies, in combination with magnetic susceptibility measurements, revealed 1 exhibits mixed valency between the radical-bearing trianionic and diamagnetic tetraanionic oxidation states of the ligand. This unpaired electron density on the ligand forms a partially occupied kagomé lattice where approximately 85% of the lattice sites are occupied with an S = ½ spin. We found that gallium mediates ferromagnetic coupling between ligand spins, creating a ferromagnetic kagomé lattice. By modulation of the interlayer spacing via post-synthetic cation metathesis of 1 to (NMe4)3.5Ga2(C6O4Cl2)3 (2) and (NEt4)2(NMe4)1.5Ga2(C6O4Cl2)3 (3), we determined the nature of the magnetic coupling between neighboring planes is antiferromagnetic. Additionally, we determined the role of the metal in mediating this magnetic coupling by comparison of 2 with the In3+ analogue, (NMe4)3.5In2(C6O4Cl2)3 (4), and we found that Ga3+ supports stronger superexchange coupling between ligand-based spins than In3+. The combination of intraplanar ferromagnetic coupling and interplanar antiferromagnetic coupling exchange interactions suggests these are promising materials to host topological phenomena.

Orbital energy mismatch engenders high-spin ground states in heterobimetallic complexes.

The spin state in heterobimetallic complexes heavily influences both reactivity and magnetism. Exerting control over spin states in main group-based heterobimetallics requires a different approach as the orbital interactions can differ substantially from that of classic coordination complexes. By deliberately engendering an energetic mismatch within the two metals in a bimetallic complex we can mimic the electronic structure of lanthanides. Towards this end, we report a new family of complexes, [Ph,MeTpMSnPh3] where M = Mn (3), Fe (4), Co (5), Ni (6), Zn (7), featuring unsupported bonding between a transition metal and Sn which represent an unusual high spin electronic structure. Analysis of the frontier orbitals reveal the desired orbital mismatch with Sn 5s/5p primarily interacting with 4s/4p M orbitals yielding localized, non-bonding d orbitals. This approach offers a mechanism to design and control spin states in bimetallic complexes.