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Li-excess Mn-based disordered rock salt oxides (DRX) are promising Li-ion cathode materials owing to their cost-effectiveness and high theoretical capacities. It has recently been shown that Mn-rich DRX Li1+xMnyM1-x-yO2 (y ≥ 0.5, M are hypervalent ions such as Ti4+ and Nb5+) exhibit a gradual capacity increase during the first few charge-discharge cycles, which coincides with the emergence of spinel-like domains within the long-range DRX structure coined as δ phase. Here, we systematically study the structural evolution upon heating of Mn-based DRX at different levels of delithiation to gain insight into the structural rearrangements occurring during battery cycling and the mechanism behind δ phase formation. We find in all cases that the original DRX structure relaxes to a δ phase, which in turn leads to capacity enhancement. Synchrotron X-ray and neutron diffraction were employed to examine the structure of the δ phase, revealing that selective migration of Li and Mn/Ti cations to different crystallographic sites within the DRX structure leads to the observed structural rearrangements. Additionally, we show that both Mn-rich (y ≥ 0.5) and Mn-poor (y < 0.5) DRX can thermally relax into a δ phase after delithiation, but the relaxation processes in these distinct compositions lead to different domain structures. Thermochemical studies and in situ heating XRD experiments further indicate that the structural relaxation has a larger thermodynamic driving force and a lower activation energy for Mn-rich DRX, as compared to Mn-poor systems, which underpins why this structural evolution is only observed for Mn-rich systems during battery cycling.

The bismuth hydride (2,6-Mes2H3C6)2BiH (1, Mes = 2,4,6-trimethylphenyl), which has a Bi-H 1H NMR spectroscopic signal at δ = 19.64 ppm, was reacted with phenylacetylene at 60 °C in toluene to yield [(2,6-Mes2C6H3)2BiC(Ph)=CH2] (2) after 15 min. Compound 2 was characterized by 1H, 13C NMR, and UV-vis spectroscopy, single crystal X-ray crystallography, and calculations employing density functional theory. Compound 2 is the first example of a hydrobismuthation addition product and displays Markovnikov regioselectivity. Computational methods indicated that it forms via a radical mechanism with an associated Gibbs energy of activation of 91 kJ mol-1 and a reaction energy of -90 kJ mol-1.

We present a wide-ranging interrogation of the border between single-molecule and solid-state magnetism through a study of erbium-based Ising-type magnetic compounds with a fixed magnetic unit, using three different charge-balancing cations as the means to modulate the crystal packing environment. Properties rooted in the isolated spin Hamiltonian remain fixed, yet careful observation of the dynamics reveals the breakdown of this approximation in a number of interesting ways. First, differences in crystal packing lead to a striking 3 orders of magnitude suppression in magnetic relaxation rates, indicating a rich interplay between intermolecular interactions governed by the anisotropic Ising lattice stabilization and localized slow magnetic relaxation driven by the spin-forbidden nature of quantum tunneling of the f-electron-based magnetization. By means of diverse and rigorous physical methods, including temperature-dependent X-ray crystallography, field, temperature, and time-dependent magnetometry, and the application of a new magnetization fitting technique to quantify the magnetic susceptibility peakshape, we are able to construct a more nuanced view of the role nonzero-dimensional interactions can play in what are predominantly considered zero-dimensional magnetic materials. Specifically, we use low field susceptibility and virgin-curve analysis to isolate metamagnetic spin-flip transitions in each system with a field strength corresponding to the expected strength of the internal dipole-dipole lattice. This behavior is vital to a complete interpretation of the dynamics and is likely common for systems with such high anisotropy. This collective interactivity opens a new realm of possibility for molecular magnetic materials, where their unprecedented localized anisotropy is the determining factor in building higher dimensionality.

The dialkyl-ortho-biaryl class of phosphines, commonly known as Buchwald-type ligands, are among the most important phosphines in Pd-catalyzed cross-coupling. These ligands have also been successfully applied to several synthetically valuable Ni-catalyzed cross-coupling methodologies and, as demonstrated in this work, are top performing ligands in Ni-catalyzed Suzuki Miyaura Coupling (SMC) and C-N coupling reactions, even outperforming commonly employed bisphosphines like dppf in many circumstances. However, little is known about their structure-reactivity relationships (SRRs) with Ni, and limited examples of well-defined, catalytically relevant Ni complexes with Buchwald-type ligands exist. In this work, we report the analysis of Buchwald-type phosphine SRRs in four representative Ni-catalyzed cross-coupling reactions. Our study was guided by data-driven classification analysis, which together with mechanistic organometallic studies of structurally characterized Ni(0), Ni(I), and Ni(II) complexes allowed us to rationalize reactivity patterns in catalysis. Overall, we expect that this study will serve as a platform for further exploration of this ligand class in organonickel chemistry as well as in the development of new Ni-catalyzed cross-coupling methodologies.

A novel mixed-valent hybrid chiral and polar compound, Fe7As3Se12(en)6(H2O), has been synthesized by a single-step solvothermal method. The crystal structure consists of 1D [Fe5Se9] chains connected via [As3Se2]-Se pentagonal linkers and charge-balancing interstitial [Fe(en)3]2+ complexes (en = ethylenediamine). Neutron powder diffraction verified that interstitial water molecules participate in the crystal packing. Magnetic polarizability of the produced compound was confirmed by X-ray magnetic circular dichroism (XMCD) spectroscopy. X-ray absorption spectroscopy (XAS) and 57Fe Mössbauer spectroscopy showed the presence of mixed-valent Fe2+/Fe3+ in the Fe-Se chains. Magnetic susceptibility measurements reveal strong antiferromagnetic nearest neighbor interactions within the chains with no apparent magnetic ordering down to 2 K. Hidden short-range magnetic ordering below 70 K was found by 57Fe Mössbauer spectroscopy, showing that a fraction of the Fe3+/Fe2+ in the chains are magnetically ordered. Nevertheless, complete magnetic ordering is not achieved even at 6 K. Analysis of XAS spectra demonstrates that the fraction of Fe3+ in the chain increases with decreasing temperature. Computational analysis points out several competing ferrimagnetic ordered models within a single chain. This competition, together with variation in the Fe oxidation state and additional weak intrachain interactions, is hypothesized to prevent long-range magnetic ordering.

The reaction of :AlAriPr8 (AriPr8 = C6H-2,6-(C6H2-2,4,6-iPr3)2-3,5-iPr2) with ArMe6N3 (ArMe6 = C6H3-2,6-(C6H2-2,4,6-Me3)2) in hexanes at ambient temperature gave the aluminum imide AriPr8AlNArMe6 (1). Its crystal structure displayed short Al-N distances of 1.625(4) and 1.628(3) Å with linear (C-Al-N-C = 180°) or almost linear (C-Al-N = 172.4(2)°; Al-N-C = 172.5(3)°) geometries. DFT calculations confirm linear geometry with an Al-N distance of 1.635 Å. According to energy decomposition analysis, the Al-N bond has three orbital components totaling -1350 kJ mol-1 and instantaneous interaction energy of -551 kJ mol-1 with respect to :AlAriPr8 and ArMe6N̈:. Dispersion accounts for -89 kJ mol-1, which is similar in strength to one Al-N π-interaction. The electronic spectrum has an intense transition at 290 nm which tails into the visible region. In the IR spectrum, the Al-N stretching band is calculated to appear at ca. 1100 cm-1. In contrast, reaction of :AlAriPr8 with 1-AdN3 or Me3SiN3 gave transient imides that immediately reacted with a second equivalent of the azide to give AriPr8Al[(NAd)2N2] (2) or AriPr8Al(N3){N(SiMe3)2} (3).

We present an extensive study of tetranuclear transition-metal cluster compounds M4(NPtBu3)4 and [M4(NPtBu3)4][B(C6F5)4] (M = Ni, Cu; tBu = tert-butyl), which feature low-coordinate metal centers and direct metal-metal orbital overlap. X-ray diffraction, electrochemical, magnetic, spectroscopic, and computational analysis elucidate the nature of the bonding interactions in these clusters and the impact of these interactions on the electronic and magnetic properties. Direct orbital overlap results in strongly coupled, large-spin ground states in the [Ni4(NPtBu3)4]+/0 clusters and fully delocalized, spin-correlated electrons. Correlated electronic structure calculations confirm the presence of ferromagnetic ground states that arise from direct exchange between magnetic orbitals, and, in the case of the neutral cluster, itinerant electron magnetism similar to that in metallic ferromagnets. The cationic nickel cluster also possesses large magnetic anisotropy exemplified by a large, positive axial zero-field splitting parameter of D = +7.95 or +9.2 cm-1, as determined by magnetometry or electron paramagnetic resonance spectroscopy, respectively. The [Ni4(NPtBu3)4]+ cluster is also the first molecule with easy-plane magnetic anisotropy to exhibit zero-field slow magnetic relaxation, and under a small applied field, it exhibits relaxation exclusively through an Orbach mechanism with a spin relaxation barrier of 16 cm-1. The S = 1/2 complex [Cu4(NPtBu3)4]+ exhibits slow magnetic relaxation via a Raman process on the millisecond time scale, supporting the presence of slow relaxation via an Orbach process in the nickel analogue. Overall, this work highlights the unique electronic and magnetic properties that can be realized in metal clusters featuring direct metal-metal orbital interactions between low-coordinate metal centers.

[Ar'SnCo]2 (1, Ar' = C6H3-2,6{C6H3-2,6- iPr2}2), a rare metal-metal bonded cobalt-tin cluster with low-coordinate tin atoms, was prepared by the reaction of [K(thf)0.2][Co(1,5-cod)2] (cod = 1,5-cyclooctadiene) with [Ar'Sn(μ-Cl)]2. This reaction illustrates a promising synthetic strategy to access uncommon metal clusters. The structure of 1 features a rhomboidal Co2Sn2 core with strong metal-metal bonds between tin and cobalt and a weaker tin-tin interaction. Reaction of 1 with white phosphorus afforded [Ar'2Sn2Co2P4] (2), the first molecular cluster compound containing phosphorus, cobalt and tin.

We report stereodivergent allylic substitution reactions of allylic esters with prochiral enolates derived from azaaryl acetamides and acetates to form products from addition of the enolates at the most substituted carbon of an allyl moiety with two catalysts, a chiral metallacyclic iridium complex and a chiral bisphosphine-ligated copper(I) complex, which individually control the configuration of the electrophilic and nucleophilic carbon atoms, respectively. By simple permutations of enantiomers of the two catalysts, all four stereoisomers of products containing two stereogenic centers were synthesized individually with high diastereoselectivity and enantioselectivity. A variety of azaaryl acetamides and acetates bearing pyridyl, benzothiazolyl, benzoxazolyl, pyrazinyl, quinolinyl and isoquinolinyl moieties were all found to be suitable for this transformation.

The key factor in long-term use of batteries is the formation of an electrically insulating solid layer that allows lithium ion transport but stops further electrolyte redox reactions on the electrode surface, hence solid electrolyte interphase (SEI). We have studied a common electrolyte, 1.0 M LiPF6/ethylene carbonate (EC)/diethyl carbonate (DEC), reduction products on crystalline silicon (Si) electrodes in a lithium (Li) half-cell system under reaction conditions. We employed in situ sum frequency generation vibrational spectroscopy (SFG-VS) with interface sensitivity in order to probe the molecular composition of the SEI surface species under various applied potentials where electrolyte reduction is expected. We found that, with a Si(100)-hydrogen terminated wafer, a Si-ethoxy (Si-OC2H5) surface intermediate forms due to DEC decomposition. Our results suggest that the SEI surface composition varies depending on the termination of Si surface, i.e., the acidity of the Si surface. We provide the evidence of specific chemical composition of the SEI on the anode surface under reaction conditions. This supports an electrochemical electrolyte reduction mechanism in which the reduction of the DEC molecule to an ethoxy moiety plays a key role. These findings shed new light on the formation mechanism of SEI on Si anodes in particular and on SEI formation in general.

DNA polymerases exhibit a surprising tolerance for analogs of deoxyribonucleoside triphosphates (dNTPs), despite the enzymes' highly evolved mechanisms for the specific recognition and discrimination of native dNTPs. Here, individual DNA polymerase I Klenow fragment (KF) molecules were tethered to a single-walled carbon nanotube field-effect transistor (SWCNT-FET) to investigate accommodation of dNTP analogs with single-molecule resolution. Each base incorporation accompanied a change in current with its duration defined by τclosed. Under Vmax conditions, the average time of τclosed was similar for all analog and native dNTPs (0.2 to 0.4 ms), indicating no kinetic impact on this step due to analog structure. Accordingly, the average rates of dNTP analog incorporation were largely determined by durations with no change in current defined by τopen, which includes molecular recognition of the incoming dNTP. All α-thio-dNTPs were incorporated more slowly, at 40 to 65% of the rate for the corresponding native dNTPs. During polymerization with 6-Cl-2APTP, 2-thio-dTTP, or 2-thio-dCTP, the nanocircuit uncovered an alternative conformation represented by positive current excursions that does not occur with native dNTPs. A model consistent with these results invokes rotations by the enzyme's O-helix; this motion can test the stability of nascent base pairs using nonhydrophilic interactions and is allosterically coupled to charged residues near the site of SWCNT attachment. This model with two opposing O-helix motions differs from the previous report in which all current excursions were solely attributed to global enzyme closure and covalent-bond formation. The results suggest the enzyme applies a dynamic stability-checking mechanism for each nascent base pair.

Effects of specific ions on the local translational diffusion of water near large hydrophilic lipid vesicle surfaces were measured by Overhauser dynamic nuclear polarization (ODNP). ODNP relies on an unpaired electron spin-containing probe located at molecular or surface sites to report on the dynamics of water protons within ~10 Å from the spin probe, which give rise to spectral densities for electron-proton cross-relaxation processes in the 10 GHz regime. This pushes nuclear magnetic resonance relaxometry to more than an order of magnitude higher frequencies than conventionally feasible, permitting the measurement of water moving with picosecond to subnanosecond correlation times. Diffusion of water within ~10 Å of, i.e., up to ~3 water layers around the spin probes located on hydrophilic lipid vesicle surfaces is ~5 times retarded compared to the bulk water translational diffusion. This directly reflects on the activation barrier for surface water diffusion, i.e., how tightly water is bound to the hydrophilic surface and surrounding waters. We find this value to be modulated by the presence of specific ions in solution, with its order following the known Hofmeister series. While a molecular description of how ions affect the hydration structure at the hydrophilic surface remains to be answered, the finding that Hofmeister ions directly modulate the surface water diffusivity implies that the strength of the hydrogen bond network of surface hydration water is directly modulated on hydrophilic surfaces.

We describe a novel epitope discovery strategy for creating an affinity agent/peptide tag pair. A synthetic polymer nanoparticle (NP) was used as the "bait" to catch an affinity peptide tag. Biotinylated peptide tag candidates of varied sequence and length were attached to an avidin platform and screened for affinity against the polymer NP. NP affinity for the avidin/peptide tag complexes was used to provide insight into factors that contribute NP/tag binding. The identified epitope sequence with an optimized length (tMel-tag) was fused to two recombinant proteins. The tagged proteins exhibited higher NP affinity than proteins without tags. The results establish that a fusion peptide tag consisting of optimized 15 amino acid residues can provide strong affinity to an abiotic polymer NP. The affinity and selectivity of NP/tMel-tag interactions were exploited for protein purification in conjunction with immobilized metal ion/His6-tag interactions to prepare highly purified recombinant proteins. This strategy makes available inexpensive, abiotic synthetic polymers as affinity agents for peptide tags and provides alternatives for important applications where more costly affinity agents are used.

Single-molecule studies of enzymes open a window into their dynamics and kinetics. A single molecule of the catalytic domain of cAMP-dependent protein kinase A (PKA) was attached to a single-walled carbon nanotube device for long-duration monitoring. The electronic recording clearly resolves substrate binding, ATP binding, and cooperative formation of PKA's catalytically functional, ternary complex. Using recordings of a single PKA molecule extending over 10 min and tens of thousands of binding events, we determine the full transition probability matrix and conversion rates governing formation of the apo, intermediate, and closed enzyme configurations. We also observe kinetic rates varying over 2 orders of magnitude from one second to another. Anti-correlation of the on and off rates for PKA binding to the peptide substrate, but not ATP, demonstrates that regulation of enzyme activity results from altering the stability of the PKA-substrate complex, not its binding to ATP. The results depict a highly dynamic enzyme offering dramatic possibilities for regulated activity, an attribute useful for an enzyme with crucial roles in cell signaling.

Bioconjugating single molecules of the Klenow fragment of DNA polymerase I into electronic nanocircuits allowed electrical recordings of enzymatic function and dynamic variability with the resolution of individual nucleotide incorporation events. Continuous recordings of DNA polymerase processing multiple homopolymeric DNA templates extended over 600 s and through >10,000 bond forming events. An enzymatic processivity of 42 nucleotides for a template of the same length was directly observed. Statistical analysis determined key kinetic parameters for the enzyme’s open and closed conformations. Consistent with these nanocircuit-based observations, the enzyme closed complex forms a phosphodiester bond in a highly efficient process >99.8% of the time with a mean duration of only 0.3 ms for all four dNTPs. The rate-limiting step for catalysis occurs during the enzyme open state, but with a nearly two-fold longer duration for dATP or dTTP incorporation than for dCTP or dGTP into complementary, homopolymeric DNA templates. Taken together, the results provide a wealth of new information complementing prior work on the mechanism and dynamics of DNA polymerase I.