Substitution Of Hydrogen Research Articles

Metal-Free C-H/C-H Coupling of 2H-Imidazole 1-Oxides with Polyphenols toward Imidazole-Linked Polyphenolic Compounds.

The methodology of nucleophilic substitution of hydrogen (SNH) was successfully applied as a convenient synthetic tool to afford azaheterocyclic derivatives of phenols of various architectures. A series of 26 novel imidazole-linked polyphenolic compounds were first prepared in 72-95% yields through the direct metal-free C-H/C-H coupling of polyphenols with 2H-imidazole 1-oxides. Comprehensive studies on the reaction condition optimization, scope, and limitations enabled the development of a straightforward method toward novel bifunctional derivatives bearing both phenolic and imidazole scaffolds of particular interest in the design of challenging molecules for versatile applications in medicinal chemistry and materials science.

Seleno-Functionalization of BODIPY Fluorophores Assisted by Oxidative Nucleophilic Hydrogen Substitution

Background: The most current reported methods of chalcogen insertion into BODIPY’s nuclei are based on nucleophilic substitution reactions of halogenated derivatives, metal-catalyzed cross-coupling reactions, or assistance by radical mechanisms. Recent reports describe Oxidative Nucleophilic Hydrogen Substitution (ONHS) reactions involving the functionalization of BODIPY nuclei by thiols, but the generalities of the strategy for other chalcogens was not yet demonstrated. Herein we report our contribution on the selenium-functionalization of BODIPY by ONHS in high yield. Objective: Aryl-Se-functionalization of 2,6-brominated BODIPY’s nuclei by ONHS reaction. Method: The procedure consists of a direct reaction of 2,6-brominated BODIPYs with in situ generated PhSeH in THF, at room temperature, under a nitrogen atmosphere. The corresponding products were isolated and purified by conventional flash column chromatography. Full structure characterization was performed by 1H, 13C, 19F, and 77Se NMR and DFT calculation. Results: Densely functionalized 2,6-dibrominated/3,5-diseleno-BODIPYs were obtained as corresponding products, leading to versatile molecular scaffolds. Their structural features were contrary to those initially expected by the original experimental applied conditions. A mechanistic investigation was performed to conclude that ONHS reaction is governing the transformation, thereby damaging the nucleophilic substitution of the halogen atoms. Conclusion: To sum up, new densely functionalized BODIPY derivatives were synthesized by a highly selective, simple, fast, metal-free, and efficient insertion of PhSe- residues into the 3,5-positions, governed by an Oxidative Nucleophilic Hydrogen Substitution (ONHS) reaction in high yields. It was observed that the presence of halogen (Br) into the 2,6-positions of the BODIPY core is mandatory for the ONHS reaction, which is completely inert when the 2,6-hydrogenated analogues are used in the same experimental conditions.

Deuterated Covalent Organic Frameworks with Significantly Enhanced Luminescence.

Luminescent covalent organic frameworks (COFs) find promising applications in chemical sensing, photocatalysis, and optoelectronic devices, however, the majority of COFs are non or weakly emissive owing to the aggregation-caused quenching (ACQ) or the molecular thermal motion-based energy dissipation. Here, we report a previously unperceived approach to improve luminescence performance of COFs by introducing isotope effect, which is achieved through substitution of hydrogen from high-frequency oscillators X-H (X=O, N, C) by heavier isotope deuterium. Combining the "bottom-up" and in situ deuteration methods generates the first deuterated COF, which exhibits an impressively 19-fold enhancement in quantum yield over that of the non-deuterated counterpart. These results are interpreted by theoretical calculations as the consequence of slower C/N-D and OD⋅⋅⋅O vibrations that impede the nonradiative deactivation process. The proposed strategy is proved applicable to many other types of emissive COFs.

Deuterated Covalent Organic Frameworks with Significantly Enhanced Luminescence

AbstractLuminescent covalent organic frameworks (COFs) find promising applications in chemical sensing, photocatalysis, and optoelectronic devices, however, the majority of COFs are non or weakly emissive owing to the aggregation‐caused quenching (ACQ) or the molecular thermal motion‐based energy dissipation. Here, we report a previously unperceived approach to improve luminescence performance of COFs by introducing isotope effect, which is achieved through substitution of hydrogen from high‐frequency oscillators X‐H (X=O, N, C) by heavier isotope deuterium. Combining the “bottom‐up” and in situ deuteration methods generates the first deuterated COF, which exhibits an impressively 19‐fold enhancement in quantum yield over that of the non‐deuterated counterpart. These results are interpreted by theoretical calculations as the consequence of slower C/N‐D and OD⋅⋅⋅O vibrations that impede the nonradiative deactivation process. The proposed strategy is proved applicable to many other types of emissive COFs.

Pyrrolizinone‐Fused BOPYINs: Characterization and Selective C‐O Bond Formation Mechanism

AbstractTwo novel pyrrolizinone‐fused BOPYINs (DAB−M and DAB−U) were prepared in one‐step through the oxidative and/or oxidative nucleophilic substitution of hydrogen (ONSH) reaction. Selective methoxyl substitution of α‐unsubstituted BOPYIN was developed, in which C−O and C=O bonds were formed and demonstrated by the single crystal structure of DAB−M. The absorption and emission spectra of both compounds showed red shift and large Stokes Shift compared with starting material DAB. Based on the TD‐DFT calculation, the electron transfer direction is totally different from DAB due to the carbonyl group on pyrrolizinone unit. Besides, a reasonable mechanism has been proposed and evidenced by quantum calculation in which the relative free energy has been exhibited.

Heterogeneous catalytic conversion of 4-chlorophenol via atomic hydrogen substitution induced by size-controlled polydisperse nanocobalt

Hyroconversion of 4-Chlorophenol (4-CP) was induced via atomic hydrogen substitution and 0.5–2 M polydisperse cobalt nanoparticles (40–500 d.nm) which were synthesized via a modified-polyol route. The cobalt nanoparticles and hydrogen incursion in the 4-CP helped to enforce the hydroconversion (HDC) reaction of 4-CP. The reaction runs were conducted based on an initial 4-CP wastewater effluent concentration discharged from a pesticide company, different particle sizes, and reaction time. Also, NaOH was added as a proton scavenger to the reaction mixture in order to avoid catalyst-deactivation. Samples from the reactor were collected at different times in order to monitor the hydroconversion process. The Co-catalyst reduced the activation energy of the reaction, initiated the hydro-substitution reaction at an earlier time, as well as enhanced 4-CP hydroconversion. Of all the catalysts, the 2 M polydisperse-cobalt nanoparticles (PD-CoNPs) gave the best performance with a description that fits the desorption mechanism whose keqd value = 0.079.

Electrooxidation Is a Promising Approach to Functionalization of Pyrazole-Type Compounds.

The review summarizes for the first time the poorly studied electrooxidative functionalization of pyrazole derivatives leading to the C–Cl, C–Br, C–I, C–S and N–N coupling products with applied properties. The introduction discusses some aspects of aromatic hydrogen substitution. Further, we mainly consider our works on effective synthesis of the corresponding halogeno, thiocyanato and azo compounds using cheap, affordable and environmentally promising electric currents.

Montmorillonite-Hydrochar Nanocomposites as Examples of Clay–Organic Interactions Delivering Ecosystem Services

AbstractClay–organic interaction is an important natural process that underpins soil ecosystem services. This process can also be tailored to produce clay–organic nanocomposites for industrial and environmental applications. The organic moiety of the nanocomposites, typically represented by a toxic surfactant, could be replaced by hydrochar formed from biomolecules (e.g. glucose) via hydrothermal carbonization. The effect of montmorillonite (Mnt) and glucose dosage on hydrochar formation, however, has not been clarified. In addition, the mechanisms by which Mnt-hydrochar nanocomposites (CMnt) can detoxify and remove carcinogenic Cr(VI) from aqueous solution are not well understood. In the current study, research milestones in terms of clay–organic interactions are summarized, following which the synthesis and characterization of CMnt for Cr(VI) adsorption are outlined. Briefly, 1 g of Mnt was reacted with 75 mL of glucose solution (0.1, 0.2, 0.3, 0.4, 0.5, and 0.6 mol L−1) by hydrothermal carbonization at 200°C for 16 h. The resultant CMnt samples were analyzed for chemical composition, functional groups, morphological features, and Cr(VI) adsorptive properties. Mnt promoted the conversion of glucose to hydrochars, the particle size of which (~80 nm) was appreciably smaller than that formed in the absence of Mnt (control). Furthermore, the hydrochars in CMnt had an aromatic structure with low hydrogen substitution and high stability (C/H atomic ratio 0.34–0.99). The weakened OH (from hydrochar) and Si–O–Si stretching peaks in the Fourier-transform infrared (FTIR) spectra of CMnt are indicative of chemical bonding between Mnt and hydrochar. The CMnt samples were effective at removing toxic Cr(VI) from acidic aqueous solutions. Several processes were involved, including direct reduction of Cr(VI) to Cr(III), complexation of Cr(III) with carboxyl and phenolic groups of hydrochar, electrostatic attraction between Cr(VI) and positively charged CMnt at pH 2 followed by indirect reduction of Cr(VI) to Cr(III), and Cr(III) precipitation.

Novel Pentafluorophenyl- and Alkoxyphenyl-Appended 2,2′-Bipyridine Push–Pull Fluorophores: A Convenient Synthesis and Photophysical Studies

AbstractA convenient method for the synthesis of new highly in non-polar solvents soluble photoactive pentafluorophenyl-substituted and extended alkoxyphenyl-substituted 2,2′-bipyridines is reported. The synthetic strategy for the preparation of such ligands involves a sequence of several structural transformations, such as O-alkylation, nucleophilic substitution of hydrogen (SN H) in 1,2,4-triazine precursors via the ‘addition–elimination’ scheme, and the subsequent conversion of the obtained 1,2,4-triazines into 2,2′-bipyridines by means of the aza-Diels–Alder reaction. The photophysical properties of the synthesized novel pentafluoroaryl-substituted 2,2′-bipyridines were comprehensively studied. The obtained photophysical data indicate the competitive advantages of the herein reported pentafluoroarylated push–pull fluorophores, bearing extended aliphatic moieties, over their analogues containing benzoxy or phenolic fragments in terms of improvement in quantum yield and well-pronounced positive solvatochromism confirmed by the mathematical analysis according to the Lippert–Mataga equation.

Benzylidene ketones as visible light radical photoinitiator: The effects of electron-donating group and co-initiator

Benzylidene ketones (BK) are promising visible photoinitiator due to their facile synthesis and photochemical hydrogen atom transfer (HAT) reaction between tertiary amines. However, the effect of electron donating (ED) groups on their photophysical, electrochemical properties, and initiation efficiency were not fully disclosed. Moreover, it is not clear which co-initiator is suitable for BK. In this work, four benzylidene ketones bearing hydrogen (C3PH), methoxy (C3PO), methylthio (C3PS), and dimethylamine (C3PN) substitution were synthesized and characterized. BK’s maximum light absorption wavelengths increase following the order of C3PH < C3PO < C3PS < C3PN. Photopolymerization and steady state photolysis show that only C3PO and C3PS display higher HAT efficiency than C3PH, which is highly relating to the free energy change calculations results. Overall, C3PO is the most efficient one because good polymerization rate and final monomer conversion can be achieved. Triethanolamine is the best co-initiator because of its low oxidation potential and the lowest energy barrier to form a complex with C3PO.

Deuterium-Grown Highly-Oriented Boron-Doped Diamond Electrodes

Boron-doped diamond (BDD) have attracted increasing attention as a material for electrochemical sensors and biosensors due to its remarkable properties such as its chemical inertness, wide electrochemical potential window, low background current and biocompatibility. Diamond layers are synthesized mainly from a gas phase consisting of carbon, hydrogen, and a dopant source by microwave plasma-assisted chemical vapour deposition (MPACVD). The gas composition during the growth of diamond film has a significant influence on its surface morphology, crystallographic structure, dopant concentration, and superficial non-diamond carbon phases. Thus, the growth conditions of the diamond layer affect the electrochemical properties of the material.Herein we demonstrate the electrochemical and physicochemical studies of as-grown boron-doped diamond thin-film electrodes, synthesized in a deuterium-rich plasma (BDDD). It is the first report concerning the study of the effect of replacing hydrogen by deuterium during BDD growth. The substitution of hydrogen to deuterium in the gas phase is primarily responsible for the enhanced boron doping and significantly decrease of nondiamond sp2 phase in diamond films. Moreover, the crystallographic structure of BDDD layer is dominated by the (111) configuration while the texture of the BDDH electrode film is oriented along the (220) direction [1].The proposed boron-doped diamonds synthesized in the deuterium-rich plasma electrodes were revealed to have a higher activity towards [Fe(CN)6]3-/4- and [Ru(NH3)6]2+/3+ redox mediators than BDD electrode grown in hydrogen-rich plasma (BDDH). The peak-to-peak separation recorded on BDDD electrode reaches 60.6 mV, and 59.8 mV in [Fe(CN)6]3-/4- and [Ru(NH3)6]2+/3+ redox couples, respectively. Moreover, in Ru(NH3)6 2+/3+ solution, the apparent heterogeneous electron transfer rate constant k° app for the BDDD was equal to 5.84·10-3 cm s-1. The BDDD and BDDH electrodes were also used as an electrochemical sensor for the paracetamol detection. BDDD electrode exhibits better sensing performance towards PCM comparing to BDDH electrode. The value of limit of detectionfor the BDDD electrode was 765 nM, whereas for the BDDH was 2510 nM. The better electrocatalytic behavior of the BDDD electrodes may result from the higher amount of electroactive zones on deuterium-terminated diamond strictly related to (111) crystal facets.AcknowledgementThis work was supported by the Polish National Science Centre [2020/01/0/ST7/00104]. The DS funds of the Faculty of Electronics, Telecommunications, and Informatics of the Gdansk University of Technology are also acknowledged.Reference:[1] A. Dettlaff et al., Carbon [In press]. Doi: doi.org/10.1016/j.carbon.2020.11.096.

Electronic and crystal structures of LnFeAsO1−x H x (Ln = La, Sm) studied by x-ray absorption spectroscopy, x-ray emission spectroscopy, and x-ray diffraction (part I: carrier-doping dependence)

A carrier doping by a hydrogen substitution in LaFeAsO1−x H x is known to cause two superconducting (SC) domes with the magnetic order at both end sides of the doping. In contrast, SmFeAsO1−x H x has a similar phase diagram but shows single SC dome. Here, we investigated the electronic and crystal structures for iron oxynitride LnFeAsO1−x H x (Ln = La, Sm) with the range of x = 0–0.5 by using x-ray absorption spectroscopy, x-ray emission spectroscopy, and x-ray diffraction. For both compounds, we observed that the pre-edge peaks of x-ray absorption spectra near the Fe-K edge were reduced in intensity on doping. The character arises from the weaker As–Fe hybridization with the longer As–Fe distance in the higher doped region. We can reproduce the spectra near the Fe-K edge according to the Anderson impurity model with realistic valence structures using the local-density approximation (LDA) plus dynamical mean-field theory (DMFT). For Ln = Sm, the integrated-absolute difference (IAD) analysis from x-ray Fe-Kβ emission spectra increases significantly. This is attributed to the enhancement of magnetic moment of Fe 3d electrons stemming from the localized picture in the higher doped region. A theoretical simulation implementing the self-consistent vertex-correction method reveals that the single dome superconducting phase for Ln = Sm arises from a better nesting condition in comparison with Ln = La.

Raman study of hydrogen-saturated silica glass

The Raman spectra of saturated solid solutions of hydrogen and deuterium in silica glass, SiO2-0.6H2 and SiO2-0.63D2, have been measured for the first time at liquid nitrogen temperature. The comparative analysis of H2 phonon modes in solid solution of hydrogen in silica glass and those of hydrogen gas shows a decrease in the frequency of rotational modes contrary to an increase in the H–H stretching vibration mode frequency. Hydrogen rotational modes, overlapped with the phonon modes of silica glass, strengthen at an elevated temperature, while the phonon modes of silica glass soften. The isotopic substitution of hydrogen by deuterium leads to a decrease in the stretching vibration mode frequency proportionally to the square root of D2/H2 mass ratio, whereas rotational mode frequencies decrease as a ratio of D2 to H2 inertia moments. The intensity of H2 phonon modes gradually decreases upon the heating of hydrogen-saturated silica glass along with the evolving of dissolved hydrogen.

Investigation of p-type doping in β- and κ-Ga2O3

We have systematically investigated the effects of all possible combinations of vacancies and silicon substitutions on the electronic structure of the β and κ phases of Ga2O3 using plane-wave density functional theory (DFT) methods. It was found that VGa defects are associated with a sufficient shift of the Fermi level to lower energy to induce p-type behavior, with formation energies in the range of 9.0 ± 0.2 eV. Calculations with single atom substitutions in the κ phase, including nitrogen, phosphorous, and silicon, did not show p-type character, although NO substitutions may lead to shallow acceptor states. In the pursuit of elucidating how MOCVD growth of Ga2O3 can result in p-type behavior, as indicated by experimental results in the literature, we examined the role of combining hydrogen and silicon substitutions. The results showed that p-type behavior is observable when gallium atoms are substituted for hydrogen within the coordination sphere of SiO substitutions. This shows that silicon can act as an amphoteric dopant for p-type Ga2O3 semiconducting materials when hydrogen is included with formation energies<6.0 eV.

Hydrogen Permeability of Epoxy Composites as Liners in Lined Rock Caverns—Experimental Study

Energy production from renewable energy sources is not stable and any fluctuations in energy productions need to be eliminated with underground energy storage. Demand of underground gas storage will be increasing, due to the switching to green energy, while the availability of underground storage sites, especially salt caverns suitable for hydrogen storage, is limited. The purpose of this paper is to compare the hydrogen permeability of different materials and select a proper liner material for hydrogen storage in Liner Rock Caverns or post mine workings. A variety of materials, like concrete, polymer concrete, epoxy resin, salt rock, and mudstone, were tested for gas permeability/hydrogen diffusion, using the combined Steady-State Flow/Carrier Gas methods. Results are shown in different units, providing the opportunity to compare the results with literature data. The permeability value of investigated epoxy resin is comparable to the salt rock (after creep process), which makes the epoxy resin a promising sealing liner for hydrogen and potential substitution of stainless-steel in Lined Rock Cavern (LRC) gas storage.

Nitrogen vacancy and hydrogen substitution mediated tunable optoelectronic properties of g-C3N4 2D layered structures: Applications towards blue LED to broad-band photodetection

Graphitic carbon nitride (g-C3N4), a 2D-organic semiconductor, has rapidly emerged as a potential alternative to the 2D-inorganic semiconductors in photocatalysis, but rare studies have been made hitherto about its applicability in optoelectronic devices. Considering the specific requirements of light-emitting diodes with efficient recombination of injected-carriers and photodetector devices with better charge separation, this work deals with synthesizing two variants of g-C3N4 samples with exclusively modified optical/electronic properties while keeping its basic structural framework. One sample is two-coordinated nitrogen deficient g-C3N4 (Nd-gCN) having very high photoluminescence (PL) and the other is hydrogen substituted g-C3N4 (H-gCN) exhibiting vanishingly low PL and ≈0.66 eV smaller bandgap than Nd-gCN. Role of nitrogen-vacancy and hydrogen substitution towards modulating optical/electronic properties of g-C3N4 are studied by combining experiments and density functional theory. Following strong luminescence, Nd-gCN sample manifests visibly blue emission in light-emitting devices; contrarily H-gCN sample shows potential in demonstrating efficient broadband photodetection. Besides moderate self-powered feature, photodetectors perform best at –5.0 V, corresponding to the highest responsivity Rλ=0.34A/W, EQEλ=59% and response time (0.18/0.29 sec). Efficient broadband photodetection performance of the heterojunction-devices is ascribed to the conjunct effects of drastic reduction in photogenerated carrier recombinations (PL quenching) and broadening of absorption regime facilitated by reduced bandgap and Si self-absorption.

Direct Amination of Nitroquinoline Derivatives via Nucleophilic Displacement of Aromatic Hydrogen.

The vicarious nucleophilic substitution of hydrogen (VNS) reaction in electron-deficient nitroquinolines was studied. Properties of all new products have been characterized by several techniques: MS, HRMS, FTIR, GC-MS, electronic absorption spectroscopy, and multinuclear NMR. The structures of 4-chloro-8-nitroquinoline, 8-(tert-butyl)-2-methyl-5-nitroquinoline, 9-(8-nitroquinolin-7-yl)-9H-carbazole and (Z)-7-(9H-carbazol-9-yl)-8-(hydroxyimino)quinolin-5(8H)-one were determined by single-crystal X-ray diffraction measurements. The 9-(8-nitroquinolin-7-yl)-9H-carbazole and (Z)-7-(9H-carbazol-9-yl)-8-(hydroxyimino)quinolin-5(8H)-one illustrate the nitro/nitroso conversion within VNS reaction. Additionally, 9-(8-isopropyl-2-((8-isopropyl-2-methyl-5-nitroquinolin-6-yl)methyl)-5-nitrosoquinolin-6-yl)-9H-carbazole is presented as a double VNS product. It is postulated that the potassium counterion interacts with the oxygen on the nitro group, which could influence nucleophile attack in that way.

A REP-FAMSEC Method as a Tool in Explaining Reaction Mechanisms: A Nucleophilic Substitution of 2-Phenylquinoxaline as a DFT Case Study.

In search for the cause leading to low reaction yields, each step along the reaction energy profile computed for the assumed oxidative nucleophilic substitution of hydrogen (ONSH) reaction between 2-phenylquinoxaline and lithium phenylacetylide was modelled computationally. Intermolecular and intramolecular interaction energies and their changes between consecutive steps of ONSH were quantified for molecular fragments playing leading roles in driving the reaction to completion. This revealed that the two reactants have a strong affinity for each other, driven by the strong attractive interactions between Li and two N-atoms, leading to four possible reaction pathways (RP-C2, RP-C3, RP-C5, and RP-C10). Four comparable in energy and stabilizing molecular system adducts were formed, each well prepared for the subsequent formation of a C–C bond at either one of the four identified sites. However, as the reaction proceeded through the TS to form the intermediates (5a–d), very high energy barriers were observed for RP-C5 and RP-C10. The data obtained at the nucleophilic addition stage indicated that RP-C3 was both kinetically and thermodynamically favored over RP-C2. However, the energy barriers observed at this stage were very comparable for both RPs, indicating that they both can progress to form intermediates 5a and 5b. Interestingly, the phenyl substituent (Ph1) on the quinoxaline guided the nucleophile towards both RP-C2 and RP-C3, indicating that the preferred RP cannot be attributed to the steric hindrance caused by Ph1. Upon the introduction of H2O to the system, both RPs were nearly spontaneous towards their respective hydrolysis products (8a and 8b), although only 8b can proceed to the final oxidation stage of the ONSH reaction mechanism. The results suggest that RP-C2 competes with RP-C3, which may lead to a possible mixture of their respective products. Furthermore, an alternative, viable, and irreversible reaction path was discovered for the RP-C2 that might lead to substantial waste. Finally, the modified experimental protocol is suggested to increase the yield of the desired product.

High Jc and low anisotropy of hydrogen doped NdFeAsO superconducting thin film

The recent realisations of hydrogen doped LnFeAsO (Ln = Nd and Sm) superconducting epitaxial thin films call for further investigation of their structural and electrical transport properties. Here, we report on the microstructure of a NdFeAs(O,H) epitaxial thin film and its temperature, field, and orientation dependencies of the resistivity and the critical current density Jc. The superconducting transition temperature Tc is comparable to NdFeAs(O,F). Transmission electron microscopy investigation supported that hydrogen is homogenously substituted for oxygen. A high self-field Jc of over 10 MA/cm2 was recorded at 5 K, which is likely to be caused by a short London penetration depth. The anisotropic Ginzburg–Landau scaling for the angle dependence of Jc yielded temperature-dependent scaling parameters γJ that decreased from 1.6 at 30 K to 1.3 at 5 K. This is opposite to the behaviour of NdFeAs(O,F). Additionally, γJ of NdFeAs(O,H) is smaller than that of NdFeAs(O,F). Our results indicate that heavily electron doping by means of hydrogen substitution for oxygen in LnFeAsO is highly beneficial for achieving high Jc with low anisotropy without compromising Tc, which is favourable for high-field magnet applications.

HoHO: A Paramagnetic Air-Resistant Ionic Hydride with Ordered Anions.

The substitution of hydrogen for oxygen atoms in metal oxides provides opportunities for influencing the solid-state properties. Such hydride oxides (or oxyhydrides) are potential functional materials and scarce. Here, we present the synthesis and characterization of holmium hydride oxide with the stoichiometric composition HoHO. It was prepared by the reaction of Ho2O3 with either HoH3 or CaH2 as a powder of light-yellow color in sunlight and pink color in artificial light (Alexandrite effect), which is commonly observed for ionic Ho(III) compounds. HoHO crystallizes with an ordered fluorite superstructure (F4̅3m, a = 5.27550(13) Å, half-Heusler LiAlSi type), as evidenced by powder X-ray and neutron powder diffraction on both hydride and deuteride and supported by quantum-mechanical calculations. HoHO is the first representative with considerable ionic bonding for this structure type. The thermal stability and inertness toward air are remarkably high for a hydride because it reacts only above 540 K to form Ho2O3. At 294(1) K and 25(3)% relative humidity, HoHO is stable for at least 3 months. HoHO is paramagnetic with μeff(Ho3+) = 10.41(2) μB without any sign of magnetic ordering down to 2 K.