Search

Despite questions about academic rigor, undergraduates use Wikipedia for opportunistic learning: self-regulated study to learn, relearn, or be introduced to concepts. STEM topics are potentially im...

The cultural geography of Bret Harte’s mining camp fiction is complex. The Gold Rush occurred in the wake of the annexation of what would become the western United States following the conflict wit...

SEA, DMD, JEH and DM thank the ERC (EU FP7 Consolidator Grant 614290 “EXONMR”) for funding. SEA would like to thank the Royal Society and the Wolfson Foundation for a merit award. The National High Magnetic Field Laboratory is supported by National Science Foundation Cooperative Agreement DMR-1644779 and the State of Florida. We present an NMR crystallographic investigation of two as-made forms of the recently characterised gallophosphate GaPO-34A, which has an unusual framework composition with a Ga : P ratio of 7 : 6 and contains both hydroxide and fluoride anions and either 1-methylimidazolium or pyridinium as the structure-directing agent. We combine previously reported X-ray crystallographic data with solid-state NMR spectroscopy and periodic density functional theory (DFT) calculations to show that the structure contains at least three distinct types of disorder (occupational, compositional and dynamic). The occupational disorder arises from the presence of six anion sites per unit cell, but a total occupancy of these of five, leading to full occupancy of four sites and partial occupancy of the fifth and sixth (which are related by symmetry). The mixture of OH and F present leads to compositional disorder on the occupied anion sites, although the occupancy of some sites by F is calculated to be energetically unfavorable and signals relating to F on these sites are not observed by NMR spectroscopy, confirming that the compositional disorder is not random. Finally, a combination of high-field 71Ga NMR spectroscopy and variable-temperature 13C and 31P NMR experiments shows that the structure directing agents are dynamic on the microsecond timescale, which can be supported by averaging the 31P chemical shifts calculated with the SDA in different orientations. This demonstrates the value of an NMR crystallographic approach, particularly in the case of highly disordered crystalline materials, where the growth of large single crystals for conventional structure determination may not be possible owing to the extent of disorder present. Postprint

This work was financially supported by the Engineering and Physical Sciences Research Council (EPSRC). This included PhD studentship to TEC (Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT), Grant code: EP/L016419/1) and to PN (Grant code EP/L505079/1). The authors would like to thank COST action SM1302 SIPs; the EPSRC UK National Mass Spectrometry Facility at Swansea University for the acquisition and processing of Mass Spectrometry Data and to EaStCHEM and the School of Chemistry for support. A series of acenaphthene species with a diisopropylphosphino group and a variety of bismuth functionalities in the peri-positions were synthesised and fully characterised, including single crystal X–ray diffraction. The majority of the reported species feature a relatively rare interpnictogen P−Bi bond. The series includes the phosphine¬−bismuthine, Acenap(PiPr2)(BiPh2) 2 (Acenap = acenaphthene-5,6-diyl), which was subjected to a fluorodearylation reaction to produce Acenap(PiPr2)(BiPhX) 5−8 and 10 (X = BF4-, Cl, Br, I, SPh), displaying varying degrees of ionicity. The geminally bis(acenaphthyl) substituted [Acenap(PiPr2)2]BiPh 3 shows a large through-space coupling of 17.8 Hz, formally 8TSJPP. Coupling deformation density (CDD) calculations confirm the double through-space coupling pathway, in which the P and Bi lone pairs mediate communication between the two 31P nuclei. Several synthetic routes towards the phosphine−diiodobismuthine Acenap(PiPr2)(BiI2) 9 have been investigated, however the purity of this, surprisingly thermally stable potential synthon, remains poor. Postprint Postprint

We provide and experimentally demonstrate an accreditation protocol that upper-bounds the variation distance between noisy and noiseless probability distributions of the outputs of arbitrary quantum computations. We accredit the outputs of twenty-four quantum circuits executed on programmable superconducting hardware, ranging from depth nine circuits on ten qubits to depth twenty-one circuits on four qubits. Our protocol requires implementing the "target" quantum circuit along with a number of random Clifford circuits and subsequently post-processing the outputs of these Clifford circuits. Importantly, the number of Clifford circuits is chosen to obtain the bound with the desired confidence and accuracy, and is independent of the size and nature of the target circuit. We thus demonstrate a practical and scalable method of ascertaining the correctness of the outputs of arbitrary-sized noisy quantum computers--the ultimate arbiter of the utility of the computer itself., Comment: Accepted version

In December 1922, when F. Scott Fitzgerald had published two successful novels and two short story collections and was generally near the height of his popularity, Metropolitan magazine brought out...

The authors would like to thank the ERC (EU FP7 Consolida-tor Grant 614290 ‘‘EXONMR’’) and EPSRC, the Collaborative Computational Project on NMR Crystallography (CCP-NC), via EP/M022501/1 and EP/J501542/1, and the United Kingdom Car-Parrinello Consortium (UKCP) via EP/P022596/1 for computational support. SEA and CJP would like to thank the Royal Society and Wolfson Foundation for merit awards. The Earth’s transition zone, at depths of 410–660 km, while being composed of nominally anhydrous magnesium silicate minerals, may be subject to significant hydration. Little is known about the mechanism of hydration, despite the vital role this plays in the physical and chemical properties of the mantle, leading to a need for improved structural characterization. Here we present an ab initio random structure searching (AIRSS) investigation of semihydrous (1.65 wt % H2O) and fully hydrous (3.3 wt % H2O) wadsleyite. Following the AIRSS process, k-means clustering was used to select sets of structures with duplicates removed, which were then subjected to further geometry optimization with tighter constraints prior to NMR calculations. Semihydrous models identify a ground-state structure (Mg3 vacancies, O1–H hydroxyls) that aligns with a number of previous experimental observations. However, predicted NMR parameters fail to reproduce low-intensity signals observed in solid-state NMR spectra. In contrast, the fully hydrous models produced by AIRSS, which enable both isolated and clustered defects, are able to explain observed NMR signals via just four low-enthalpy structures: (i) a ground state, with isolated Mg3 vacancies and O1–H hydroxyls; (ii/iii) edge-sharing Mg3 vacancies with O1–H and O3–H species; and (iv) edge-sharing Mg1 and Mg3 vacancies with O1–H, O3–H, and O4–H hydroxyls. Thus, the combination of advanced structure searching approaches and solid-state NMR spectroscopy is able to provide new and detailed insight into the structure of this important mantle mineral. Publisher PDF

Purpose To present the visual and safety outcomes of surgery for primary idiopathic macular holes including predictors of visual acuity and the impact of combined phacovitrectomy surgery. Design Registry-style, prospective, nonrandomized, observational cohort study. Participants Patients with idiopathic macular holes undergoing primary surgery. Methods Surgeons were invited to submit clinical details of all macular hole cases receiving surgery. Baseline demographic and clinical information, and details of surgical intervention were collected. Primary follow-up data were collected at 3 months postoperatively or before revision surgery, and surgeons were also asked to submit data at 12 and 24 months postoperatively. Main Outcome Measures Visual acuity improvement ≥15 letters and ≥0 letters, change in mean visual acuity, visual acuity ≥70 letters (20/40), retinal detachment, and endophthalmitis. Results A total of 2455 eyes of 2366 patients were included in the study, and hole closure was achieved in 95.6% of eyes with a single procedure. Mean baseline vision was 48.3 letters. The proportion of successful eyes improving ≥15 letters at 3, 12, and 24 months was 59.1%, 69.4%, and 68.2%, respectively. The mean improvement in acuity at 3, 12, and 24 months was 16.0, 19.2, and 23.6 letters, and 92.4%, 93.4%, and 95.8% improved ≥0 letters at 3, 12, and 24 months, respectively. Eyes receiving SF6 gas had better visual acuities at all time points postoperatively (adjusted effect 3.4, 3.1, and 4.6 letters better at 3, 12, and 24 months vs. longer-acting gas, respectively). Combined phacovitrectomy in phakic eyes was associated with better corrected visual acuity postoperatively (vs. vitrectomy surgery alone), a difference that vanished when eyes went on to have subsequent cataract surgery. The rate of retinal detachment postoperatively was 1.3%, and the odds of detachment were greater in eyes receiving longer-acting gases versus SF6 gas (adjusted odds ratio, 2.2; 95% confidence interval, 1.04–4.77; P = 0.039). There were no reported cases of endophthalmitis. Conclusions Macular hole surgery substantially improved acuity in approximately two thirds of patients and was seldom associated with loss of vision. SF6 gas was associated with better visual outcomes, an effect that warrants further study.

How Are Christians To Serve Christ At This Point In History? We Approach The Question From The Perspective Of Faith In A Sovereign God, Not In Pessimism Or Defeatism. While Activity Is Required, God’s Chief Concern Is With Being Rather Than Doing. We Ask First, “Who Are We?” Identity Is Not Self-generated But Given By God. Christians Are Christlike People— Redeemed, Indwelt By The Holy Spirit, Loving, And Holy. They Are Also A Covenant Community—united With The Triune God And With One Another. We Then Ask, “What Should We Be Doing?” After Repenting Of Our Failures, We Are, According To Our Particular Callings And Contexts, Sent To Preach The Word, Spread The Gospel, Engage With Society, And Endure Persecution. KEYWORDS

Supplementary material for the preprint "Experimental accreditation of outputs of noisy quantum computers". Contains: - Experimental data. - Notebooks to analyse the data and generate the circuits.

Characterising the local structures (e.g., the cation distribution) of mixed-metal ceramics by NMR spectroscopy is often challenging owing to the unfavourable properties (low γ, large quadrupole moment and/or low abundance) of many metal nuclei.

Improving two-qubit gate performance and suppressing crosstalk are major, but often competing, challenges to achieving scalable quantum computation. In particular, increasing the coupling to realize faster gates has been intrinsically linked to enhanced crosstalk due to unwanted two-qubit terms in the Hamiltonian. Here, we demonstrate a novel coupling architecture for transmon qubits that circumvents the standard relationship between desired and undesired interaction rates. Using two fixed frequency coupling elements to tune the dressed level spacings, we demonstrate an intrinsic suppression of the static $ZZ$, while maintaining large effective coupling rates. Our architecture reveals no observable degradation of qubit coherence ($T_1,T_2 > 100~��s$) and, over a factor of 6 improvement in the ratio of desired to undesired coupling. Using the cross-resonance interaction we demonstrate a 180~ns single-pulse CNOT gate, and measure a CNOT fidelity of 99.77(2)$\%$ from interleaved randomized benchmarking., 5 pages, 3 figures plus supplement (4 pages, 3 figures)

The authors would like to thank the ERC (EU FP7 Consolidator Grant 614290 EXONMR and Advanced Grant 787073 ADOR), and EPSRC (EP/N509759/1) for a studentship for CMR. SEA would like to thank the Royal Society and Wolfson Foundation for a merit award. We acknowledge support from the Collaborative Computational Project on NMR Crystallography (CCP-NC) funded by EPSRC (EP/M022501/1) and the UKCP consortium funded by EPSRC (EP/K013564/1). For computational resources we are grateful to the UK Materials and Molecular Modelling Hub, which is partially funded by EPSRC (EP/P020194/1) and the UK HPC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202). The research data (and/or materials) supporting this publication can be accessed at DOI: https://doi.org/10.17630/31529c8b-f197-484c-929b-ef993a5bea68.69 The breathing behaviour of 17O-enriched (Al,Ga)-MIL-53, a terephthalate-based metal organic framework, has been investigated using a combination of solid-state nuclear magnetic resonance (NMR) spectroscopy, powder X-ray diffraction (PXRD) and first-principles calculations. These reveal that the behaviour observed for as-made, calcined, hydrated and subsequently dehydrated mixed-metal MIL-53 materials differs with composition, but cannot be described as the compositionally weighted average of the breathing behaviour seen for the two end members. Although the form of MIL-53 adopted by the as-made material is independent of metal composition, upon calcination, materials with higher levels of Al adopt an open pore (OP) form, as found for the Al end member, but substitution of Ga results in mixed pore materials, with OP and narrow pore (NP) forms co-existing. Although the Ga end member is prone to decomposition under the calcination conditions used, a low level of Al in the starting synthesis (5%) leads to an OP mixed-metal MOF that is stable to calcination. Upon hydration all materials almost exclusively adopt a closed pore (CP) structure, with strong hydrogen bonding interactions with water leading to two distinct resonances from the carboxylate oxygens in 17O NMR spectra. When dehydrated, different framework structures are found for the two end members, OP for Al- MIL-53 and NP for Ga-MIL-53, with the proportion of NP MOF seen to increase systematically with the Ga content in mixed-metal materials, in contrast to the forms seen upon initial calcination. 17O NMR spectra of mixed-metal MIL-53 materials show an increased preference for clustering of like cations as the Ga content increases. This is not a result of the small-scale dry gel conversion reactions used for enrichment, as a similar cation distribution and clustering is also observed for (Al0.5,Ga0.5)-MIL-53 synthesised hydrothermally and enriched with 17O via post-synthetic steaming. Publisher PDF

The breathing behaviour of 17O-enriched (Al,Ga)-MIL-53, a terephthalate-based metal-organic framework, has been investigated using a combination of solid-state nuclear magnetic resonance (NMR) spectroscopy, powder X-ray diffraction (PXRD) and first-principles calculations. These reveal that the behaviour observed for as-made, calcined, hydrated and subsequently dehydrated mixed-metal MIL-53 materials differs with composition, but cannot be described as the compositionally weighted average of the breathing behaviour seen for the two end members. Although the form of MIL-53 adopted by the as-made material is independent of metal composition, upon calcination, materials with higher levels of Al adopt an open pore (OP) form, as found for the Al end member, but substitution of Ga results in mixed pore materials, with OP and narrow pore (NP) forms co-existing. Although the Ga end member is prone to decomposition under the calcination conditions used, a low level of Al in the starting synthesis (5%) leads to an OP mixed-metal MOF that is stable to calcination. Upon hydration, all materials almost exclusively adopt a closed pore (CP) structure, with strong hydrogen bonding interactions with water leading to two distinct resonances from the carboxylate oxygens in 17O NMR spectra. When dehydrated, different framework structures are found for the two end members, OP for Al-MIL-53 and NP for Ga-MIL-53, with the proportion of NP MOF seen to increase systematically with the Ga content in mixed-metal materials, in contrast to the forms seen upon initial calcination. 17O NMR spectra of mixed-metal MIL-53 materials show an increased preference for clustering of like cations as the Ga content increases. This is not a result of the small-scale dry gel conversion reactions used for enrichment, as a similar cation distribution and clustering is also observed for (Al0.5,Ga0.5)-MIL-53 synthesised hydrothermally and enriched with 17O via post-synthetic steaming.

Reducing measurement errors in multi-qubit quantum devices is critical for performing any quantum algorithm. Here we show how to mitigate measurement errors by a classical post-processing of the measured outcomes. Our techniques apply to any experiment where measurement outcomes are used for computing expected values of observables. Two error mitigation schemes are presented based on tensor product and correlated Markovian noise models. Error rates parameterizing these noise models can be extracted from the measurement calibration data using a simple formula. Error mitigation is achieved by applying the inverse noise matrix to a probability vector that represents the outcomes of a noisy measurement. The error mitigation overhead, including the the number of measurements and the cost of the classical post-processing, is exponential in $\epsilon n$, where $\epsilon$ is the maximum error rate and $n$ is the number of qubits. We report experimental demonstration of our error mitigation methods on IBM Quantum devices using stabilizer measurements for graph states with $n\le 12$ qubits and entangled 20-qubit states generated by low-depth random Clifford circuits., Comment: 13 pages, 7 figures

We present a comprehensive theoretical study of the cross-resonance gate operation covering estimates for gate parameters and gate error as well as analyzing spectator qubits and multi-qubit frequency collisions. We start by revisiting the derivation of effective Hamiltonian models following Magesan et al. (arXiv:1804.04073). Transmon qubits are commonly modeled as a weakly anharmonic Kerr oscillator. Kerr theory only accounts for qubit frequency renormalization, while adopting number states as the eigenstates of the bare qubit Hamiltonian. Starting from the Josephson nonlinearity and by accounting for the eigenstates renormalization, due to counter-rotating terms, we derive a new starting model for the cross-resonance gate with modified qubit-qubit interaction and drive matrix elements. Employing time-dependent Schrieffer-Wolff perturbation theory, we derive an effective Hamiltonian for the cross-resonance gate with estimates for the gate parameters calculated up to the fourth order in drive amplitude. The new model with renormalized eigenstates lead to 10-15 percent relative correction of the effective gate parameters compared to Kerr theory. We find that gate operation is strongly dependent on the ratio of qubit-qubit detuning and anharmonicity. In particular, we characterize five distinct regions of operation, and propose candidate parameter choices for achieving high gate speed and low coherent gate error when the cross-resonance tone is equipped with an echo pulse sequence. Furthermore, we generalize our method to include a third spectator qubit and characterize possible detrimental multi-qubit frequency collisions., 30 pages, 15 figures and 4 tables

An 18-qubit GHZ state with multipartite entanglement is prepared and measured on a 20-qubit device. The detection technique used, which is based on measuring multiple quantum coherences, is robust to noise and only requires measuring the population in the ground state.

Crosstalk is a major source of noise in Noisy Intermediate-Scale Quantum (NISQ) systems and is a fundamental challenge for hardware design. When multiple instructions are executed in parallel, crosstalk between the instructions can corrupt the quantum state and lead to incorrect program execution. Our goal is to mitigate the application impact of crosstalk noise through software techniques. This requires (i) accurate characterization of hardware crosstalk, and (ii) intelligent instruction scheduling to serialize the affected operations. Since crosstalk characterization is computationally expensive, we develop optimizations which reduce the characterization overhead. On three 20-qubit IBMQ systems, we demonstrate two orders of magnitude reduction in characterization time (compute time on the QC device) compared to all-pairs crosstalk measurements. Informed by these characterization, we develop a scheduler that judiciously serializes high crosstalk instructions balancing the need to mitigate crosstalk and exponential decoherence errors from serialization. On real-system runs on three IBMQ systems, our scheduler improves the error rate of application circuits by up to 5.6x, compared to the IBM instruction scheduler and offers near-optimal crosstalk mitigation in practice. In a broader picture, the difficulty of mitigating crosstalk has recently driven QC vendors to move towards sparser qubit connectivity or disabling nearby operations entirely in hardware, which can be detrimental to performance. Our work makes the case for software mitigation of crosstalk errors., Comment: To appear in ASPLOS 2020

Hardware efficient transpilation of quantum circuits to a quantum devices native gateset is essential for the execution of quantum algorithms on noisy quantum computers. Typical quantum devices utilize a gateset with a single two-qubit Clifford entangling gate per pair of coupled qubits, however, in some applications access to a non-Clifford two-qubit gate can result in more optimal circuit decompositions and also allows more flexibility in optimizing over noise. We demonstrate calibration of a low error non-Clifford Controlled-$\frac{\pi}{2}$ phase (CS) gate on a cloud based IBM Quantum computing using the Qiskit Pulse framework. To measure the gate error of the calibrated CS gate we perform non-Clifford CNOT-Dihedral interleaved randomized benchmarking. We are able to obtain a gate error of $5.9(7) \times 10^{-3}$ at a gate length 263 ns, which is close to the coherence limit of the associated qubits, and lower error than the backends standard calibrated CNOT gate., Comment: 9 pages, 4 figures, references are updated, QPT curve in the Fig. 2 is updated based on new analysis procedure detailed in Appendix B. Conclusions unchanged

Mitigating crosstalk errors, whether classical or quantum mechanical, is critically important for achieving high-fidelity entangling gates in multi-qubit circuits. For weakly anharmonic superconducting qubits, unwanted $ZZ$ interactions can be suppressed by combining qubits with opposite anharmonicity. We present experimental measurements and theoretical modeling of two-qubit gate error for gates based on the cross resonance interaction between a capacitively shunted flux qubit and a transmon and demonstrate the elimination of the $ZZ$ interaction., 5+16 pages, 5+13 figures, corrected typos, hyperlinking fixed, modified sections in supplement

R.E.M. thanks the Royal Society and the EPSRC (Grants EP/L014475/1, EP/K025112/1) for funding work in this area and the Czech Science Foundation for the project P106/12/G015 and OP VVV “Excellent Research Teams”, project No. CZ.02.1.01/0.0/0.0/15_003/0000417 – CUCAM. SEA thanks the Royal Society/Wolfson Foundation for a merit award, and the European Research Council (EU FP7 Consolidator Grant 614290 “EXONMR”) for funding. This research used resources of the Advanced Light Source, which is a US DOE Office of Science User Facility under contract no. DE-AC02-05CH11231 and the development of the gas cell used in this research was funded through US DOE award # DE-SC0001015. We also thank Diamond Light Source and Chiu Tang for access to beamline I11. We thank Mr Simon Vornholt for help with the electron microscopy and the EPSRC Capital for Great Technologies funding (EP/L017008/1). Highly porous metal–organic frameworks (MOFs), which have undergone exciting developments over the past few decades, show promise for a wide range of applications. However, many studies indicate that they suffer from significant stability issues, especially with respect to their interactions with water, which severely limits their practical potential. Here we demonstrate how the presence of ‘sacrificial’ bonds in the coordination environment of its metal centres (referred to as hemilability) endows a dehydrated copper-based MOF with good hydrolytic stability. On exposure to water, in contrast to the indiscriminate breaking of coordination bonds that typically results in structure degradation, it is non-structural weak interactions between the MOF’s copper paddlewheel clusters that are broken and the framework recovers its as-synthesized, hydrated structure. This MOF retained its structural integrity even after contact with water for one year, whereas HKUST-1, a compositionally similar material that lacks these sacrificial bonds, loses its crystallinity in less than a day under the same conditions. Postprint Postprint

Funding: ERC (EU FP7 Consolidator Grant 614290 ‘‘EXONMR’’). Royal Society and Wolfson Foundation merit award (SEA). We acknowledge support from the Collaborative Computational Project on NMR Crystallography CCP-NC funded by EPSRC (EP/M022501/1) and the UKCP consortium funded by EPSRC (EP/K013564/1). For computational resources we are grateful to the UK Materials and Molecular Modelling Hub, which is partially funded by EPSRC (EP/P020194/1), and to the UK HPC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202). The sensitivity of NMR to the local environment, without the need for any long-range order, makes it an ideal tool for the characterization of disordered materials. Computational prediction of NMR parameters can be of considerable help in the interpretation and assignment of NMR spectra of solids, but the statistical representation of all possible chemical environments for a solid solution is challenging. Here, we illustrate the use of a symmetry-adapted configurational ensemble in the simulation of NMR spectra, in combination with solid-state NMR experiments. We show that for interpretation of the complex and overlapped lineshapes that are typically observed, it is important to go beyond a single-configuration representation or a simple enumeration of local environments. The ensemble method leads to excellent agreement between simulated and experimental spectra for Y2(Sn,Ti)2O7 pyrochlore ceramics, where the overlap of signals from different local environments prevents a simple decomposition of the experimental spectral lineshapes. The inclusion of a Boltzmann weighting confirms that the best agreement with experiment is obtained at higher temperatures, in the limit of full disorder. We also show that to improve agreement with experiment, in particular at low dopant concentrations, larger supercells are needed, which might require alternative simulation approaches as the complexity of the system increases. It is clear that ensemble-based modeling approaches in conjunction with NMR spectroscopy offer great potential for understanding configurational disorder, ultimately aiding the future design of functional materials. Publisher PDF

The sensitivity of NMR to the local environment, without the need for any long-range order, makes it an ideal tool for the characterization of disordered materials. Computational prediction of NMR parameters can be of considerable help in the interpretation and assignment of NMR spectra of solids, but the statistical representation of all possible chemical environments for a solid solution is challenging. Here, we illustrate the use of a symmetry-adapted configurational ensemble in the simulation of NMR spectra, in combination with solid-state NMR experiments. We show that for interpretation of the complex and overlapped lineshapes that are typically observed, it is important to go beyond a single-configuration representation or a simple enumeration of local environments. The ensemble method leads to excellent agreement between simulated and experimental spectra for Y2(Sn,Ti)2O7 pyrochlore ceramics, where the overlap of signals from different local environments prevents a simple decomposition of the experimental spectral lineshapes. The inclusion of a Boltzmann weighting confirms that the best agreement with experiment is obtained at higher temperatures, in the limit of full disorder. We also show that to improve agreement with experiment, in particular at low dopant concentrations, larger supercells are needed, which might require alternative simulation approaches as the complexity of the system increases. It is clear that ensemble-based modeling approaches in conjunction with NMR spectroscopy offer great potential for understanding configurational disorder, ultimately aiding the future design of functional materials.

We would like to thank the ERC (EU FP7 Consolidator Grant 614290 “EXONMR”) and EPSRC for computational support through the Collaborative Computational Project on NMR Crystallography (CCP-NC), via EP/M022501/1 and EP/J010510/1. SEA would like to thank the Royal Society and the Wolfson Foundation for a merit award. The research data (and/or materials) supporting this publication can be accessed at DOI: 10.17630/d0b365a1-b647-4556-b6f8-24d99d0c7a8a. A series of P−E‐containing heterocycles (E=chalcogen) with aromatic backbones were synthesised and characterised by single‐crystal and powder XRD, microanalysis and mass spectrometry. Solution‐ and solid‐state 31P and 77Se NMR spectroscopy revealed significant differences between the NMR parameters in solution and in the solid state, related to conformational changes in the molecules. Many compounds were shown to exhibit a number of different polymorphic structures (identified by single‐crystal XRD), although the bulk material studied by solid‐state NMR spectroscopy often contained just one major polymorph. For the unoxidised heterocycles, the presence of weak intermolecular J couplings was also investigated by DFT calculations. Publisher PDF

The authors thank the ERC (EU FP7 Consolidator Grant 614290 “EXONMR”), and EPSRC (EP/K025112/1, EP/L014475/1 and EP/M506631/1 (for GPMB)). SEA would like to thank the Royal Society and the Wolfson Foundation for a merit award. The UK 850 MHz solid-state NMR Facility used in this research was funded by EPSRC and BBSRC (contract reference PR140003), as well as the University of Warwick including via part funding through Birmingham Science City Advanced Materials Projects 1 and 2 supported by Advantage West Midlands (AWM) and the European Regional Development Fund (ERDF). 17O solid-state NMR spectroscopy is employed to investigate the cation disorder in metal–organic frameworks containing two different types of metal cations. Although NMR offers exquisite sensitivity to the local, atomic-scale structure, making it an ideal tool for the characterisation of disordered materials, the low natural abundance of 17O (0.037%) necessitates expensive isotopic enrichment to acquire spectra on a reasonable timescale. Using dry gel conversion and a novel steaming method we show that cost-effective and atom-efficient enrichment of MOFs is possible, and that high-resolution 17O NMR spectra are sensitive both to the structural forms of the MOF and the presence of guest molecules. For mixed-metal forms of MIL-53, NMR can also provide information on the final composition of the materials (notably different to that of the initial starting material) and the preference for cation clustering/ordering within the MOFs. For Al, Ga MIL-53, the distribution of cations results in a mixed-pore form upon exposure to water, unlike the different structures seen for the corresponding end members. This work shows that as good levels of enrichment can be achieved at reasonable cost, 17O NMR spectroscopy should be an invaluable tool for the study of these important functional materials. Publisher PDF