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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.

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 (

Metal–ligand covalency enables observation of coherent spin dynamics to room temperature in a series of vanadium(iv) and copper(ii) catechol complexes., Harnessing synthetic chemistry to design electronic spin-based qubits, the smallest unit of a quantum information system, enables us to probe fundamental questions regarding spin relaxation dynamics. We sought to probe the influence of metal–ligand covalency on spin–lattice relaxation, which comprises the upper limit of coherence time. Specifically, we studied the impact of the first coordination sphere on spin–lattice relaxation through a series of four molecules featuring V–S, V–Se, Cu–S, and Cu–Se bonds, the Ph4P+ salts of the complexes [V(C6H4S2)3]2– (1), [Cu(C6H4S2)2]2– (2), [V(C6H4Se2)3]2– (3), and [Cu(C6H4Se2)2]2– (4). The combined results of pulse electron paramagnetic resonance spectroscopy and ac magnetic susceptibility studies demonstrate the influence of greater M–L covalency, and consequently spin-delocalization onto the ligand, on elongating spin–lattice relaxation times. Notably, we observe the longest spin–lattice relaxation times in 2, and spin echos that survive until room temperature in both copper complexes (2 and 4).

Developing the field of quantum information science (QIS) hinges upon designing viable qubits, the smallest unit in quantum computing. One approach to creating qubits is introducing paramagnetic defects into semiconductors or insulators. This class of qubits has seen success in the form of nitrogen-vacancy centers in diamond, divacancy defects in SiC, and P doped into Si. These materials feature paramagnetic defects in a low nuclear spin environment to reduce the impact of nuclear spin on electronic spin coherence. In this work, we report single crystal growth of Ba$_2$CaWO$_{6-��}$, and the coherence properties of controllably introduced W$^{5+}$ spin centers generated by oxygen vacancies. Ba$_2$CaWO$_{6-��}$ ($��$ = 0) is a B-site ordered double perovskite with a temperature-dependent octahedral tilting wherein oxygen vacancies generate W$^{5+}$ (d$^1$), $S = \frac{1}{2}, I$ = 0, centers. We characterized these defects by measuring the spin-lattice ($T_1$) and spin-spin relaxation ($T_2$) times from T = 5 to 150 K. At T = 5 K, $T_1$ = 310 ms and $T_2$ = 4 $��$s, establishing the viability of these qubit candidates. With increasing temperature, $T_2$ remains constant up to T = 60 K and then decreases to $T_2$ $\approx$ 1 $��$s at T = 90 K, and remains roughly constant until T = 150 K, demonstrating the remarkable stability of $T_2$ with increasing temperature. Together, these results demonstrate that controlled defect generation in double perovskite structures can generate viable paramagnetic point centers for quantum applications and expand the field of potential materials for QIS., 9 pages, 5 figures

Metal–organic frameworks enable the synthesis of arrays of atomically precise qubits., Synthetic chemistry offers a pathway to realize atomically precise arrays of qubits, the smallest unit of a quantum information science system. We harnessed framework chemistry to create an array of qubit candidates, featuring one qubit every 13.6 Å, by synthesizing the new copper(ii) variant of the porphyrinic metal–organic framework PCN-224. We subjected the framework to pulse-electron paramagnetic resonance (EPR) measurements, establishing spin coherence at temperatures up to 80 K within a fully spin concentrated framework. Observation of Rabi oscillations further support the viability of the qubits within these arrays. To interrogate the spin dynamics of qubit arrays, we investigated spin–lattice relaxation, T1, through a combination of pulse-EPR and alternating current (ac) magnetic susceptibility measurements. These data revealed distinct vibrational environments within the frameworks that contribute to spin dynamics. The aggregate results establish a pathway for a synthetic approach to create spatially precise networks of qubits.

We employ ac susceptibility as a probe of small changes of transverse zero-field splitting, revealing that these subtle changes transform [Co(C3S5)2]2– from a molecular magnet to a candidate qubit., Mononuclear transition metal complexes demonstrate significant potential in the divergent applications of spintronics and quantum information processing. The facile tunability of these complexes enables structure function correlations for a plethora of relevant magnetic quantities. We present a series of pseudotetrahedral [Co(C3S5)2]2– complexes with varying deviations from D2d symmetry to investigate the influence of structural distortions on spin relaxation dynamics and qubit viability, as tuned by the variable transverse magnetic anisotropy, E. To overcome the traditional challenge of measuring E in species where D ≫ E, we employed a different approach of harnessing ac magnetic susceptibility to probe the emergence of quantum tunneling of magnetization as a proxy for E. Across the range of values for E in the series, we observe magnetic hysteresis for the smallest value of E. The hysteresis disappears with increasing E, concomitant with the appearance of an observable, low frequency (L-band) electron paramagnetic resonance (EPR) signal, indicating the potential to controllably shift the molecule's utilization from classical to quantum information processing applications. The development of design principles for molecular magnet information processing requires separate design principles for classical versus quantum regimes. Here we show for the first time how subtle structural changes can switch the utility of a complex between these two types of applications.