Multiconfigurational Electronic Structure of Nickel Cross-Coupling Catalysts Revealed by X-ray Absorption Spectroscopy.

Ni 2,2'-bipyridine complexes are commonly invoked intermediates in metallaphotoredox cross-coupling reactions. Despite their ubiquity, design principles targeting improved catalytic performance remain underdetermined. A series of Ni(bpy)(Ar)Cl (R = MeOOC, -Bu, R' = CH, CF) complexes were proposed to have multiconfigurational electronic structures on the basis of multiconfigurational/multireference calculations, with significant mixing of Ni → bpy metal-to-ligand charge transfer (MLCT) configurations into the ground-state wave function.

Ultrafast all-optical coherence of molecular electron spins in room-temperature water solution.

The tunability and spatial precision of paramagnetic molecules makes them attractive for quantum sensing. However, usual microwave-based detection methods have poor temporal and spatial resolution, and optical methods compatible with room-temperature solutions have remained elusive. In this study, we utilized pump-probe polarization spectroscopy to initialize and track electron spin coherence in a molecule.

Mechanisms of Photoredox Catalysis Featuring Nickel-Bipyridine Complexes.

Metallaphotoredox catalysis can unlock useful pathways for transforming organic reactants into desirable products, largely due to the conversion of photon energy into chemical potential to drive redox and bond transformation processes. Despite the importance of these processes for cross-coupling reactions and other transformations, their mechanistic details are only superficially understood. In this review, we have provided a detailed summary of various photoredox mechanisms that have been proposed to date for Ni-bipyridine (bpy) complexes, focusing separately on photosensitized and direct excitation reaction processes.

Alternant Hydrocarbon Diradicals as Optically Addressable Molecular Qubits.

High-spin molecules allow for bottom-up qubit design and are promising platforms for magnetic sensing and quantum information science. Optical addressability of molecular electron spins has also been proposed in first-row transition-metal complexes via optically detected magnetic resonance (ODMR) mechanisms analogous to the diamond-nitrogen-vacancy color center. However, significantly less progress has been made on the front of metal-free molecules, which can deliver lower costs and milder environmental impacts.

Determining the key vibrations for spin relaxation in ruffled Cu(ii) porphyrins resonance Raman spectroscopy.

Pinpointing vibrational mode contributions to electron spin relaxation () constitutes a key goal for developing molecular quantum bits (qubits) with long room-temperature coherence times. However, there remains no consensus to date as to the energy and symmetry of the relevant modes that drive relaxation. Here, we analyze a series of three geometrically-tunable = ½ Cu(ii) porphyrins with varying degrees of ruffling distortion in the ground state.

Anisotropy Elucidates Spin Relaxation Mechanisms in an = 1 Cr(IV) Optically Addressable Molecular Qubit.

Paramagnetic molecules offer unique advantages for quantum information science owing to their spatial compactness, synthetic tunability, room-temperature quantum coherence, and potential for optical state initialization and readout. However, current optically addressable molecular qubits are hampered by rapid spin-lattice relaxation () even at sub-liquid nitrogen temperatures. Here, we use temperature- and orientation-dependent pulsed electron paramagnetic resonance (EPR) to elucidate the negative sign of the ground state zero-field splitting (ZFS) and assign anisotropy to specific types of motion in an optically addressable = 1 Cr(-tolyl) molecular qubit.

Electronic Structures of Nickel(II)-Bis(indanyloxazoline)-dihalide Catalysts: Understanding Ligand Field Contributions That Promote C(sp)-C(sp) Cross-Coupling.

dihalide [ = (3a,3a',8a,8a')-2,2'-(cyclopropane-1,1-diyl)bis(3a,8a-dihydro-8-indeno[1,2-]-oxazole)] complexes are representative of a growing class of first-row transition-metal catalysts for the enantioselective reductive cross-coupling of C(sp) and C(sp) electrophiles. Recent mechanistic studies highlight the complexity of these ground-state cross-couplings but also illuminate new reactivity pathways stemming from one-electron redox and their significant sensitivities to reaction conditions. For the first time, a diverse array of spectroscopic methods coupled to electrochemistry have been applied to Ni-based precatalysts to evaluate specific ligand field effects governing key Ni-based redox potentials.

Photogenerated Ni(I)-Bipyridine Halide Complexes: Structure-Function Relationships for Competitive C(sp)-Cl Oxidative Addition and Dimerization Reactivity Pathways.

We report the facile photochemical generation of a library of Ni(I)-bpy halide complexes (Ni(I)(bpy)X (R = -Bu, H, MeOOC; X = Cl, Br, I) and benchmark their relative reactivity toward competitive oxidative addition and off-cycle dimerization pathways. Structure-function relationships between the ligand set and reactivity are developed, with particular emphasis on rationalizing previously uncharacterized ligand-controlled reactivity toward high energy and challenging C(sp)-Cl bonds. Through a dual Hammett and computational analysis, the mechanism of the formal oxidative addition is found to proceed through an SAr-type pathway, consisting of a nucleophilic two-electron transfer between the Ni(I) 3() orbital and the C-Cl σ* orbital, which contrasts the mechanism previously observed for activation of weaker C(sp)-Br/I bonds.

Illuminating Ligand Field Contributions to Molecular Qubit Spin Relaxation via Anisotropy.

Electron spin relaxation in paramagnetic transition metal complexes constitutes a key limitation on the growth of molecular quantum information science. However, there exist very few experimental observables for probing spin relaxation mechanisms, leading to a proliferation of inconsistent theoretical models. Here we demonstrate that spin relaxation anisotropy in pulsed electron paramagnetic resonance is a powerful spectroscopic probe for molecular spin dynamics across a library of highly coherent Cu(II) and V(IV) complexes.

Bootstrap methods for quantifying the uncertainty of binding constants in the hard modeling of spectrophotometric titration data.

Equilibrium hard modeling of spectrophotometric titration data with binding parameters (ΔG° or logK values) involves nonlinear mathematical relationships and correlated experimental uncertainties. Therefore, uncertainty quantification techniques based on standard error computation substantially underestimate the true error for the calculated binding parameters. We show that the bootstrapping technique can provide accurate uncertainty quantification with no a priori knowledge of experimental error levels.

Hard Ferromagnetism Down to the Thinnest Limit of Iron-Intercalated Tantalum Disulfide.

Two-dimensional (2D) magnetic crystals hold promise for miniaturized and ultralow power electronic devices that exploit spin manipulation. In these materials, large, controllable magnetocrystalline anisotropy (MCA) is a prerequisite for the stabilization and manipulation of long-range magnetic order. In known 2D magnetic crystals, relatively weak MCA typically results in soft ferromagnetism.

Elucidating the Mechanism of Excited-State Bond Homolysis in Nickel-Bipyridine Photoredox Catalysts.

Ni 2,2'-bipyridine (bpy) complexes are commonly employed photoredox catalysts of bond-forming reactions in organic chemistry. However, the mechanisms by which they operate are still under investigation. One potential mode of catalysis is via entry into Ni(I)/Ni(III) cycles, which can be made possible by light-induced, excited-state Ni(II)-C bond homolysis.

The Impact of Ligand Field Symmetry on Molecular Qubit Coherence.

Developing quantum bits (qubits) exhibiting room temperature electron spin coherence is a key goal of molecular quantum information science. At high temperatures, coherence is often limited by electron spin relaxation, measured by . Here we develop a simple and powerful model for predicting relative relaxation times in transition metal complexes from dynamic ligand field principles.

Strain fields in twisted bilayer graphene.

Van der Waals heteroepitaxy allows deterministic control over lattice mismatch or azimuthal orientation between atomic layers to produce long-wavelength superlattices. The resulting electronic phases depend critically on the superlattice periodicity and localized structural deformations that introduce disorder and strain. In this study we used Bragg interferometry to capture atomic displacement fields in twisted bilayer graphene with twist angles <2°.

Deconvolving Contributions to Decoherence in Molecular Electron Spin Qubits: A Dynamic Ligand Field Approach.

In the past decade, transition metal complexes have gained momentum as electron spin-based quantum bit (qubit) candidates due to their synthetic tunability and long achievable coherence times. The decoherence of magnetic quantum states imposes a limit on the use of these qubits for quantum information technologies, such as quantum computing, sensing, and communication. With rapid recent development in the field of molecular quantum information science, a variety of chemical design principles for prolonging coherence in molecular transition metal qubits have been proposed.