Thermodynamically Stable Functionalization of Microporous Aromatic Frameworks with Sulfonic Acid Groups by Inserting Methylene Spacers.

Porous aromatic frameworks (PAFs) are an auspicious class of materials that allow for the introduction of sulfonic acid groups at the aromatic core units by post-synthetic modification. This makes PAFs promising for proton-exchange materials. However, the limited thermal stability of sulfonic acid groups attached to aromatic cores prevents high-temperature applications. Here, we present a framework based on PAF-303 where the acid groups were added as methylene sulfonic acid side chains in a two-step post-synthetic route (SMPAF-303) via the intermediate chloromethylene PAF (ClMPAF-303). Elemental analysis, NMR spectroscopy, electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy were used to characterize both frameworks and corroborate the successful attachment of the side chains. The resulting framework SMPAF-303 features high thermal stability and an ion-exchange capacity of about 1.7 mequiv g-1. The proton conductivity depends strongly on the adsorbed water level. It reaches from about 10-7 S cm-1 for 33% RH to about 10-1 S cm-1 for 100% RH. We attribute the strong change to a locally alternating polarity of the inner surfaces. The latter introduces bottleneck effects for the water molecule and oxonium ion diffusion at lower relative humidities, due to electrolyte clustering. When the pores are completely filled with water, these bottlenecks vanish, leading to an unhindered electrolyte diffusion through the framework, explaining the conductivity rise.

Na2C3O2: The First Crystalline Compound with the Elusive -C≡C-COO- Anion.

By reaction of sodium electride or NaC2H with the anhydrous sodium salt of propiolic acid, Na(OOC-C≡C-H), in liquid ammonia crystalline powders of Na2C3O2 were obtained. The structure analysis based on synchrotron powder diffraction data revealed that Na2C3O2 crystallizes in a monoclinic unit cell (I2/a, Z=4) exhibiting the elusive Y-shaped -C≡C-COO- anion, which is unprecedented in a crystalline compound up to now. IR/Raman and solid-state NMR spectroscopic investigations with assignments supported by DFT-based ab initio calculations confirm this finding. Reaction with sodium electride led to a higher crystallinity of the product, but additionally a by-product apparently due to decomposition and polymerization of Na2C3O2 was formed. No such by-product was observed in the reaction with NaC2H, which turned out to be a milder metalation route. However, the product of the latter reaction is less crystalline.

Ultrafast Proton Conduction in an Aqueous Electrolyte Confined in Adamantane-like Micropores of a Sulfonated, Aromatic Framework.

Sulfonated, cross-linked porous polymers are promising frameworks for aqueous high-performance electrolyte-host systems for electrochemical energy storage and conversion. The systems offer high proton conductivities, excellent chemical and mechanical stabilities, and straightforward water management. However, little is known about mass transport mechanisms in such nanostructured hosts. We report on the synthesis and postsynthetic sulfonation of an aromatic framework (SPAF-2) with a 3D-interconnected nanoporosity and varying sulfonation degrees. Water adsorption produces the system SPAF-2H20. It features proton exchange capacities up to 6 mequiv g-1 and exceptional proton conductivities of about 1 S cm-1. Two contributions are essential for the highly efficient transport. First, the nanometer-sized pores link the charge transport to the diffusion of adsorbed water molecules, which is almost as fast as bulk water. Second, continuous exchange between interface-bound and mobile species enhances the conductivities at elevated temperatures. SPAF-2H20 showcases how to tailor nanostructured electrolyte-host systems with liquid-like conductivities.

Porous Salts Containing Cationic Al24 -Hydroxide-Acetate Clusters from Scalable, Green and Aqueous Synthesis Routes.

The solution chemistry of aluminum is highly complex and various polyoxocations are known. Here we report on the facile synthesis of a cationic Al24 cluster that forms porous salts of composition [Al24 (OH)56 (CH3 COO)12 ]X4 , denoted CAU-55-X, with X=Cl- , Br- , I- , HSO4 - . Three-dimensional electron diffraction was employed to determine the crystal structures. Various robust and mild synthesis routes for the chloride salt [Al24 (OH)56 (CH3 COO)12 ]Cl4 in water were established resulting in high yields (>95 %, 215 g per batch) within minutes. Specific surface areas and H2 O capacities with maximum values of up to 930 m2 g-1 and 430 mg g-1 are observed. The particle size of CAU-55-X can be tuned between 140 nm and 1250 nm, permitting its synthesis as stable dispersions or as highly crystalline powders. The positive surface charge of the particles, allow fast and effective adsorption of anionic dye molecules and adsorption of poly- and perfluoroalkyl substances (PFAS).

Delamination by Repulsive Osmotic Swelling of Synthetic Na-Hectorite with Variable Charge in Binary Dimethyl Sulfoxide-Water Mixtures.

Swelling of clays is hampered by increasing layer charge. With vermiculite-type layer charge densities, crystalline swelling is limited to the two-layer hydrate, while osmotic swelling requires ion exchange with bulky and hydrophilic organic molecules or with Li+ cations to trigger repulsive osmotic swelling. Here, we report on surprising and counterintuitive osmotic swelling behavior of a vermiculite-type synthetic clay [Na0.7]inter[Mg2.3Li0.7]oct[Si4]tetO10F2 in mixtures of water and dimethyl sulfoxide (DMSO). Although swelling in pure water is restricted to crystalline swelling, with the addition of DMSO, osmotic swelling sets in at some threshold composition. Finally, when the DMSO concentration is increased further to 75 vol %, swelling is restricted again to crystalline swelling as expected. Repulsive osmotic swelling thus is observed in a narrow composition range of the binary water-DMSO mixture, where a freezing point suppression is observed. This suppression is related to DMSO and water molecules exhibiting strong interactions leading to stable molecular clusters. Based on this phenomenological observation, we hypothesize that the unexpected swelling behavior might be related to the formation of different complexes of interlayer cations being formed at different compositions. Powder X-ray diffraction and 23Na magic angle spinning-NMR evidence is presented that supports this hypothesis. We propose that the synergistic solvation of the interlayer sodium at favorable compositions exerts a steric pressure by the complexes formed in the interlayer. Concomitantly, the basal spacing is increased to a level, where entropic contributions of interlayer species lead to a spontaneous thermodynamically allowed one-dimensional dissolution of the clay stack.

Investigation of the Thermal Stability of Proteinase K for the Melt Processing of Poly(l-lactide).

The enzymatic degradation of aliphatic polyesters offers unique opportunities for various use cases in materials science. Although evidently desirable, the implementation of enzymes in technical applications of polyesters is generally challenging due to the thermal lability of enzymes. To prospectively overcome this intrinsic limitation, we here explored the thermal stability of proteinase K at conditions applicable for polymer melt processing, given that this hydrolytic enzyme is well established for its ability to degrade poly(l-lactide) (PLLA). Using assorted spectroscopic methods and enzymatic assays, we investigated the effects of high temperatures on the structure and specific activity of proteinase K. Whereas in solution, irreversible unfolding occurred at temperatures above 75-80 °C, in the dry, bulk state, proteinase K withstood prolonged incubation at elevated temperatures. Unexpectedly little activity loss occurred during incubation at up to 130 °C, and intermediate levels of catalytic activity were preserved at up to 150 °C. The resistance of bulk proteinase K to thermal treatment was slightly enhanced by absorption into polyacrylamide (PAM) particles. Under these conditions, after 5 min at a temperature of 200 °C, which is required for the melt processing of PLLA, proteinase K was not completely denatured but retained around 2% enzymatic activity. Our findings reveal that the thermal processing of proteinase K in the dry state is principally feasible, but equally, they also identify needs and prospects for improvement. The experimental pipeline we establish for proteinase K analysis stands to benefit efforts directed to this end. More broadly, our work sheds light on enzymatically degradable polymers and the thermal processing of enzymes, which are of increasing economical and societal relevance.

Portable Hyperpolarized Xe-129 Apparatus with Long-Time Stable Polarization Mediated by Adaptable Rb Vapor Density.

The extraordinary sensitivity of 129Xe, hyperpolarized by spin-exchange optical pumping, is essential for magnetic resonance imaging and spectroscopy in life and materials sciences. However, fluctuations of the polarization over time still limit the reproducibility and quantification with which the interconnectivity of pore spaces can be analyzed. Here, we present a polarizer that not only produces a continuous stream of hyperpolarized 129Xe but also maintains stable polarization levels on the order of hours, independent of gas flow rates. The polarizer features excellent magnetization production rates of about 70 mL/h and 129Xe polarization values on the order of 40% at moderate system pressures. Key design features include a vertically oriented, large-capacity two-bodied pumping cell and a separate Rb presaturation chamber having its own temperature control, independent of the main pumping cell oven. The separate presaturation chamber allows for precise control of the Rb vapor density by restricting the Rb load and varying the temperature. The polarizer is both compact and transportable─making it easily storable─and adaptable for use in various sample environments. Time-evolved two-dimensional (2D) exchange spectra of 129Xe absorbed in the microporous metal-organic framework CAU-1-AmMe are presented to highlight the quantitative nature of the device.

Crystal Engineering of Supramolecular 1,4-Benzene Bisamides by Side-Chain Modification - Towards Tuneable Anisotropic Morphologies and Surfaces.

Benzene bisamides are promising building blocks for supramolecular nano-objects. Their functionality depends on morphology and surface properties. However, a direct link between surface properties and molecular structure itself is missing for this material class. Here, we investigate this interplay for two series of 1,4-benzene bisamides with symmetric and asymmetric peripheral substitution. We elucidated the crystal structures, determined the nano-object morphologies and derived the wetting behaviour of the preferentially exposed surfaces. The crystal structures were solved by combining single-crystal and powder X-ray diffraction, solid-state NMR spectroscopy and computational modelling. Bulky side groups, here t-butyl groups, serve as a structure-directing motif into a packing pattern, which favours the formation of thin platelets. The use of slim peripheral groups on both sides, in our case linear perfluorinated, alkyl chains, self-assemble the benzene bisamides into a second packing pattern which leads to ribbon-like nano-objects. For both packing types, the preferentially exposed surfaces consist of the ends of the peripheral groups. Asymmetric substitution with bulky and slim groups leads to an ordered alternating arrangement of the groups exposed to the surface. This allows the hydrophobicity of the surfaces to be gradually altered. We thus identified two leitmotifs for molecular packings of benzene bisamides providing the missing link between the molecular structure, the anisotropic morphologies and adjustable surface properties of the supramolecular nano-objects.

Reconstructing the Environmental Degradation of Polystyrene by Accelerated Weathering.

The fragmentation of macro- into microplastics (MP) is the main source of MP in the environment. Nevertheless, knowledge about degradation mechanisms, changes in chemical composition, morphology, and residence times is still limited. Here, we present a long-term accelerated weathering study on polystyrene (PS) tensile bars and MP particles using simulated solar radiation and mechanical stress. The degradation process was monitored by gel permeation chromatography (GPC), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), 13C magic-angle spinning (MAS) NMR spectroscopy, tensile testing, and Monte Carlo simulations. We verified that degradation proceeds in two main stages. Stage I is dominated by photooxidation in a near-surface layer. During stage II, microcrack formation and particle rupturing accelerate the degradation. Depending on the ratio and intensity of the applied stress factors, MP degradation kinetics and lifetimes vary dramatically and an increasing amount of small MP fragments with high proportions of carboxyl, peroxide, and keto groups is continuously released into the environment. The enhanced surface area for adsorbing pollutants and forming biofilms modifies the uptake behavior and interaction with organisms together with potential ecological risks. We expect the proposed two-stage model to be valid for predicting the abiotic degradation of other commodity plastics with a carbon-carbon backbone.

Solvent Impact on the Properties of Benchmark Metal-Organic Frameworks: Acetonitrile-Based Synthesis of CAU-10, Ce-UiO-66, and Al-MIL-53.

Herein is reported the utilization of acetonitrile as a new solvent for the synthesis of the three significantly different benchmark metal-organic frameworks (MOFs) CAU-10, Ce-UiO-66, and Al-MIL-53 of idealized composition [Al(OH)(ISO)], [Ce6 O4 (OH)4 (BDC)6 ], and [Al(OH)(BDC)], respectively (ISO2- : isophthalate, BDC2- : terephthalate). Its use allowed the synthesis of Ce-UiO-66 on a gram scale. While CAU-10 and Ce-UiO-66 exhibit properties similar to those reported elsewhere for these two materials, the obtained Al-MIL-53 shows no structural flexibility upon adsorption of hydrophilic or hydrophobic guest molecules such as water and xenon and is stabilized in its large-pore form over a broad temperature range (130-450 K). The stabilization of the large-pore form of Al-MIL-53 was attributed to a high percentage of noncoordinating -COOH groups as determined by solid-state NMR spectroscopy. The defective material shows an unusually high water uptake of 310 mg g-1 within the range of 0.45 to 0.65 p/p°. In spite of showing no breathing effect upon water adsorption it exhibits distinct mechanical properties. Thus, mercury intrusion porosimetry studies revealed that the solid can be reversibly forced to breathe by applying moderate pressures (≈60 MPa).

La3 B6 O13 (OH): The First Acentric High-Pressure Borate Displaying Edge-Sharing BO4 Tetrahedra.

La3 B6 O13 (OH) was obtained by a high-pressure/high-temperature experiment at 6 GPa and 1673 K. The compound crystallizes in the space group P21 (no. 4) with the lattice parameters a=4.785(2), b=12.880(4), c=7.433(3) Å, and ß=90.36(10)°, and is built up of corner- as well as edge-sharing BO4 tetrahedra. It represents the first acentric high-pressure borate containing these B2 O6 entities. The compound develops borate layers of "sechser"-rings with the La3+ cations positioned between the layers. Single-crystal and powder X-ray diffraction, vibrational and MAS NMR spectroscopy, second-harmonic generation (SHG) and thermoanalytical measurements, as well as computational methods were used to affirm the proposed structure and the B2 O6 entities.

Design and Precursor-based Solid-State Synthesis of Mixed-Linker Zr-MIL-140A.

Acetic acid, an alternative green solvent, was utilized for the solvothermal synthesis of four 2D materials of composition [Zr2O2(OAc)2(BDC-F)], [Zr2O2(OAc)2(BDC-F4)], [Zr2O2(OAc)2(BDC)], and [Zr2O2(OAc)2(NDC)] (BDC, terephthalate; BDC-F, 2-fluoroterephthalate; BDC-F4, tetrafluoroterephthalate; NDC, 2,6-naphthalenedicarboxylate). The first three compounds were subsequently reacted with terephthalic acid in solid-state reactions to form porous MIL-140A-type metal-organic frameworks and mixed-linker derivatives ([ZrO(BDC)1-x(BDC-Y)x], x = 0-0.18, Y = F, F4). The reaction kinetics of the formation of MIL-140A were investigated with the aid of time-resolved synchrotron and temperature-resolved in-house X-ray powder diffraction experiments. Thorough compositional analyses and solid-state NMR spectroscopic experiments were used to assess the crystallographic ordering of the different linker molecules. Additionally, acetic acid-based routes for the direct synthesis of MIL-140A-NO2 and a novel MIL-140A-(CH3)2 derivative were discovered.

Reorientational dynamics of trimethoxyboroxine: A molecular glass former studied by dielectric spectroscopy and 11B nuclear magnetic resonance.

In this work, trimethoxyboroxine (TMB) is identified as a small-molecule glass former. In its viscous liquid as well as glassy states, static and dynamic properties of TMB are explored using various techniques. It is found that, on average, the structure of the condensed TMB molecules deviates from threefold symmetry so that TMB's electric dipole moment is nonzero, thus rendering broadband dielectric spectroscopy applicable. This method reveals the super-Arrhenius dynamics that characterizes TMB above its glass transition, which occurs at about 204 K. To extend the temperature range in which the molecular dynamics can be studied, 11B nuclear magnetic resonance experiments are additionally carried out on rotating and stationary samples: Exploiting dynamic second-order shifts, spin-relaxation times, line shape effects, as well as stimulated-echo and two-dimensional exchange spectroscopy, a coherent picture regarding the dynamics of this glass former is gained.

Microporous Organically Pillared Layered Silicates (MOPS): A Versatile Class of Functional Porous Materials.

The design of microporous hybrid materials, tailored for diverse applications, is a key to address our modern society's imperative of sustainable technologies. Prerequisites are flexible customization of host-guest interactions by incorporating various types of functionality and by adjusting the pore structure. On that score, metal-organic frameworks (MOFs) have been the reference in the past decades. More recently, a new class of microporous hybrid materials emerged, microporous organically pillared layered silicates (MOPS). MOPS are synthesized by simple ion exchange of organic or metal complex cations in synthetic layered silicates. MOFs and MOPSs share the features of "component modularity" and "functional porosity". While both, MOFs and MOPS maintain the intrinsic characteristics of their building blocks, new distinctive properties arise from their assemblage. MOPS are unique since allowing for simultaneous and continuous tuning of micropores in the sub-Ångström range. Consequently, with MOPS the adsorbent recognition may be optimized without the need to explore different framework topologies. Similar to the third generation of MOFs (also termed soft porous crystals), MOPS are structurally ordered, permanently microporous solids that may also show a reversible structural flexibility above a distinct threshold pressure of certain adsorbents. This structural dynamism of MOPS can be utilized by meticulously adjusting the charge density of the silicate layers to the polarizability of the adsorbent leading to different gate opening mechanisms. The potential of MOPS is far from being fully explored. This Concept article highlights the main features of MOPS and illustrates promising directions for further research.

Synthesis, Crystal Structure, and Selected Properties of [Au(S2 CNH2 )2 ]SCN: A Precursor for Gold Macro-Needles Consisting of Gold Nanoparticles Glued by Graphitic Carbon Nitride.

A new preparation route is developed for the synthesis of needle-like crystals of [Au(S2 CNH2 )2 ]SCN, which avoids disproportionation of the AuI salt used as a starting material. In the crystal structure, the two crystallographically independent AuIII centers are in a square-planar environment of two S2 CNH2 ligands. The Hirshfeld surface analysis reveals the presence of noncovalent intermolecular S⋅⋅⋅S interactions, which are essential for the spatial arrangement of the molecules. Density functional theory (DFT) calculations including dispersion and damping corrections result in a unit cell volume very close to the value determined experimentally. Thermal decomposition in an inert atmosphere generates black needles with lengths of up to 500 µm. X-ray powder diffraction and pair distribution function analyses demonstrate that the needles are composed of nanosized crystals with a volume-weighted average domain size of 20(1) nm. According to results of X-ray photoemission experiments, the black needles are covered by a nitrogen-rich carbon nitride with composition near (CN)2 N. 13 C solid-state NMR investigations indicate that two different carbon species are present, with signals corresponding well to heptazine units as in melon and triazine units as in poly(triazin imide) type compounds. Scanning transmission electron microscopy tomography evidences that the needles are composed of slightly elongated nanoparticles.

Elucidating the formation of Al-NBO bonds, Al-O-Al linkages and clusters in alkaline-earth aluminosilicate glasses based on molecular dynamics simulations.

Exploring the reasons for the initiation of Al-O-Al bond formation in alkali-earth alumino silicate glasses is a key topic in the glass-science community. Evidence for the formation of Al-O-Al and Al-NBO bonds in the glass composition 38.7CaO-9.7MgO-12.9Al2O3-38.7SiO2 (CMAS, mol%) has been provided based on Molecular Dynamics (MD) simulations. Analyses in the short-range order confirm that silicon and the majority of aluminium cations form regular tetrahedra. Well-separated homonuclear (Si-O-Si) and heteronuclear (Si-O-Al) cluster regions have been identified. In addition, a channel region (C-Region), separated from the network region, enriched with both NBO and non-framework modifier cations, has also been identified. These findings are in support of the previously proposed extended modified random network (EMRN) model for aluminosilicate glasses. A detailed analysis of the structural distributions revealed that a majority of Al, 51.6%, is found in Si-O-Al links. Although the formation of Al-O-Al and Al-NBO bonds is energetically less favourable, a significant amount of Al is found in Al-O-Al links (33.5%), violating Lowenstein's rule, and the remainder is bonded with non-bridging oxygen (NBO) in the form of Al-NBO (Al-O-(Ca, Mg)). The conditions necessary for the formation of less favourable bonds are attributed to the presence of a high amount of modifier cations in current CMAS glass and their preferable coordination.

Exploring Local Disorder within CAU-1 Frameworks Using Hyperpolarized 129Xe NMR Spectroscopy.

The sorption properties of metal-organic frameworks (MOFs) can be influenced by introducing covalently attached functional side chains, which make this subclass of porous materials promising for applications as diverse as gas storage and separation, catalysis, and drug delivery. The incorporation of side groups usually comes along with disorder, as the synthesis procedures rarely allow for one specific position among a larger group of equivalent sites to be selected. For a series of isoreticular CAU-1 frameworks, chosen as model compounds, one out of four positions at every linker is modified with equal probability. Here, we investigate the influence of this disorder on Ar sorption and 129Xe nuclear magnetic resonance spectroscopy using hyperpolarized 129Xe gas. Models used for predicting the pore dimensions as well as their distributions were derived from the unfunctionalized framework by replacing one proton at every linker with either an amino, an acetamide, or a methyl urea functionality. The resulting structures were optimized using density functional theory (DFT) calculations. Results from void analyses and Monte Carlo force field simulations suggest that for available Ar nonlocal DFT (NLDFT) kernels, neither the pore dimensions nor the distributions induced by the side-chain disorder are well-reproduced. By contrast, we found the 129Xe chemical shift analysis for the shift observed at high temperature to be well-suited to develop a detailed fingerprint of the porosity and side-chain disorder within the isoreticular CAU-1 series. After calibrating the 129Xe limiting shift of the amino-functionalized framework with DFT calculations, the downfield shifts for the other two derivatives are an excellent measure for the reduction of the accessible pore space and reveal a strong preference for the side chains toward the octahedral voids for both cases. We expect that the strategy presented here can be commonly applied to disorder phenomena within MOFs in the future.

Quantitative description of 1H SQ and DQ coherences for the hydroxyl disorder within hydrous ringwoodite.

Proton-containing point defects in solid materials are important for a variety of properties ranging from ionic transport over thermal conductivity up to compressibility. Ultrafast magic-angle spinning techniques nowadays offer high-resolution solid-state NMR spectra, even for 1H, and thus open up possibilities to study the underlying defect chemistry. Nevertheless, disorder within such defects again leads to heavy spectral overlap of 1H resonances, which prevents quantitative analysis of defect concentrations, if several defect types are present. Here, we present a strategy to overcome this limitation by simulating the 1H lineshape as well as 1H-1H double-quantum buildup curves, which we then validate against the experimental data in a joint cost function. To mimic the local structural disorder, we use molecular dynamics simulations at the DFT level. It turned out to be advantageous for the joint refinement to put the computational effort into the structural optimisation to derive accurate proton positions and to use empirical correlations for the relation between isotropic and anisotropic 1H chemical shifts and structural elements. The expressiveness of this approach is demonstrated on ringwoodite's (γ-Mg2SiO4) OH defect chemistry containing four different defect types in octahedral and tetrahedral voids with both pure Mg and mixed Si and Mg cation environments. Still, we determine the ratio for each defect type with an accuracy of about 5% as a result of the minimization of the joint cost function. We expect that our approach is generally applicable for local proton disorder and might prove to be a valuable alternative to the established AIRSS and Monte Carlo methods, respectively.

Synthesis and Characterization of Cs4 Ga6 Q11 (Q=S, Se): Chalcogenometalates with Exotic Polymeric Anions.

Two new chalcogenogallates Cs4 Ga6 Q11 (Q=S, Se) were obtained by a controlled thermal treatment of CsN3 in the presence of stoichiometric amounts of Ga2 Q3 and the elemental chalcogens at elevates temperatures. Both isotypic compounds crystallize in the space group P 1 ‾ (no. 2). The most prominent structural feature in these chalcogenogallates are the complex anionic Dreier double chains 1 ∞ [Ga6 Q11 4- ] formed by condensed GaQ4 tetrahedra. The semiconductors Cs4 Ga6 S11 (Eg =3.14 eV) and Cs4 Ga6 Se11 (Eg =2.41 eV) were further studied by using UV/Vis, 133 Cs and 71 Ga solid-state NMR spectroscopy, and complementary DFT calculations. The 133 Cs MAS NMR spectra are characteristic for cationic cesium and vibrational spectra show two distinct regions, attributed to the Ga-Q valence and deformation vibrations, respectively. High-temperature studies revealed incongruent melting of both solids, which is also depicted in updated binary phase-diagrams Cs2 Q-Ga2 Q3 (Q=S, Se).

Hidden Oceans? Unraveling the Structure of Hydrous Defects in the Earth's Deep Interior.

High-pressure silicates making up the main proportion of the earth's interior can incorporate a significant amount of water in the form of OH defects. Generally, they are charge balanced by removing low-valent cations such as Mg2+. By combining high-resolution multidimensional single- and double-quantum 1H solid-state NMR spectroscopy with density functional theory calculations, we show that, for ringwoodite (γ-Mg2SiO4), additionally, Si4+ vacancies are formed, even at a water content as low as 0.1 wt %. They are charge balanced by either four protons or one Mg2+ and two protons. Surprisingly, also a significant proportion of coupled Mg and Si vacancies are present. Furthermore, all defect types feature a pronounced orientational disorder of the OH groups, which results in a significant range of OH···O bond distributions. As such, we are able to present unique insight into the defect chemistry of ringwoodite's spinel structure, which not only accounts for a potentially large fraction of the earth's entire water budget, but will also control transport properties in the mantle. We expect that our results will even impact other hydrous spinel-type materials, helping to understand properties such as ion conduction and heterogeneous catalysis.