Controlling the Superconductivity of Nb2PdxS5 via Reversible Li Intercalation.

The Nb2PdxS5 (x ≈ 0.74) superconductor with a Tc of 6.5 K is reduced by the intercalation of lithium in ammonia solution or electrochemically to produce an intercalated phase with expanded lattice parameters. The structure expands by 2% in volume and maintains the C2/m symmetry and rigidity due to the PdS4 units linking the layers. Experimental and computational analysis of the chemically synthesized bulk sample shows that Li occupies triangular prismatic sites between the layers with an occupancy of 0.33(4). This level of intercalation suppresses the superconductivity, with the injection of electrons into the metallic system observed to also reduce the Pauli paramagnetism by ∼40% as the bands are filled to a Fermi level with a lower density of states than in the host material. Deintercalation using iodine partially restores the superconductivity, albeit at a lower Tc of ∼5.5 K and with a smaller volume fraction than in fresh Nb2PdxS5. Electrochemical intercalation reproduces the chemical intercalation product at low Li content (<0.4) and also enables greater reduction, but at higher Li contents (≥0.4) accessed by this route, phase separation occurs with the indication that Li occupies another site.

Structures and Magnetic Ordering in Layered Cr Oxide Arsenides Sr2CrO2Cr2OAs2 and Sr2CrO3CrAs.

Two novel chromium oxide arsenide materials have been synthesized, Sr2CrO2Cr2OAs2 (i.e., Sr2Cr3As2O3) and Sr2CrO3CrAs (i.e., Sr2Cr2AsO3), both of which contain chromium ions in two distinct layers. Sr2CrO2Cr2OAs2 was targeted following electron microscopy measurements on a related phase. It crystallizes in the space group P4/mmm and accommodates distorted CrO4As2 octahedra containing Cr2+ and distorted CrO2As4 octahedra containing Cr3+. In contrast, Sr2CrO3CrAs incorporates Cr3+ in CrO5 square-pyramidal coordination in [Sr2CrO3]+ layers and Cr2+ ions in CrAs4 tetrahedra in [CrAs]- layers and crystallizes in the space group P4/nmm. Powder neutron diffraction data reveal antiferromagnetic ordering in both compounds. In Sr2CrO3CrAs the Cr2+ moments in the [CrAs]- layers exhibit long-range ordering, while the Cr3+ moments in the [Sr2CrO3]+ layers only exhibit short-range ordering. However, in Sr2CrO2Cr2OAs2, both the Cr2+ moments in the CrO4As2 environments and the Cr3+ moments in the CrO2As4 polyhedra are long-range-ordered below 530(10) K. Above this temperature, only the Cr3+ moments are ordered with a Néel temperature slightly in excess of 600 K. A subtle structural change is evident in Sr2CrO2Cr2OAs2 below the magnetic ordering transitions.

Magnetic Ordering in the Layered Cr(II) Oxide Arsenides Sr2CrO2Cr2As2 and Ba2CrO2Cr2As2.

Sr2CrO2Cr2As2 and Ba2CrO2Cr2As2 with Cr2+ ions in CrO2 sheets and in CrAs layers crystallize with the Sr2Mn3Sb2O2 structure (space group I4/mmm, Z = 2) and lattice parameters a = 4.00800(2) Å, c = 18.8214(1) Å (Sr2CrO2Cr2As2) and a = 4.05506(2) Å, c = 20.5637(1) Å (Ba2CrO2Cr2As2) at room temperature. Powder neutron diffraction reveals checkerboard-type antiferromagnetic ordering of the Cr2+ ions in the arsenide layers below TN1_Sr, of 600(10) K (Sr2CrO2Cr2As2) and TN1_Ba 465(5) K (Ba2CrO2Cr2As2) with the moments initially directed perpendicular to the layers in both compounds. Checkerboard-type antiferromagnetic ordering of the Cr2+ ions in the oxide layer below 230(5) K for Ba2CrO2Cr2As2 occurs with these moments also perpendicular to the layers, consistent with the orientation preferences of d4 moments in the two layers. In contrast, below 330(5) K in Sr2CrO2Cr2As2, the oxide layer Cr2+ moments are initially oriented in the CrO2 plane; but on further cooling, these moments rotate to become perpendicular to the CrO2 planes, while the moments in the arsenide layers rotate by 90° with the moments on the two sublattices remaining orthogonal throughout [behavior recently reported independently by Liu et al. [Liu et al. Phys. Rev. B 2018, 98, 134416]]. In Sr2CrO2Cr2As2, electron diffraction and high resolution powder X-ray diffraction data show no evidence for a structural distortion that would allow the two Cr2+ sublattices to couple, but high resolution neutron powder diffraction data suggest a small incommensurability between the magnetic structure and the crystal structure, which may account for the coupling of the two sublattices and the observed spin reorientation. The saturation values of the Cr2+ moments in the CrO2 layers (3.34(1) µB (for Sr2CrO2Cr2As2) and 3.30(1) µB (for Ba2CrO2Cr2As2)) are larger than those in the CrAs layers (2.68(1) µB for Sr2CrO2Cr2As2 and 2.298(8) µB for Ba2CrO2Cr2As2) reflecting greater covalency in the arsenide layers.

Expression Patterns of Genes Encoding Sugar and Potassium Transport Proteins Are Simultaneously Upregulated or Downregulated When Carbon and Potassium Availability Is Modified in Shiraz (Vitis vinifera L.) Berries.

A link between the accumulation of sugar and potassium has previously been described for ripening grape berries. The functional basis of this link has, as of yet, not been elucidated but could potentially be associated with the integral role that potassium has in phloem transport. An experiment was conducted on Shiraz grapevines in a controlled environment. The accumulation of berry sugar was curtailed by reducing the leaf photoassimilation rate, and the availability of potassium was increased through soil fertilization. The study characterizes the relationship between the accumulation of sugar and potassium into the grape berry and describes how their accumulation patterns are related to the expression patterns of their transporter proteins. A strong connection was observed between the accumulation of sugar and potassium in the grape berry pericarp, irrespective of the treatment. The relative expression of proteins associated with sugar and potassium transport across the tonoplast and plasma membrane was closely correlated, suggesting transcriptional coregulation leading to the simultaneous translocation and storage of potassium and sugar in the grape berry cell.

Synthesis, Structure, and Compositional Tuning of the Layered Oxide Tellurides Sr2MnO2Cu2- xTe2 and Sr2CoO2Cu2Te2.

The synthesis and structure of two new transition metal oxide tellurides, Sr2MnO2Cu1.82(2)Te2 and Sr2CoO2Cu2Te2, are reported. Sr2CoO2Cu2Te2 with the purely divalent Co2+ ion in the oxide layers has magnetic ordering based on antiferromagnetic interactions between nearest neighbors and appears to be inert to attempted topotactic oxidation by partial removal of the Cu ions. In contrast, the Mn analogue with the more oxidizable transition metal ion has a 9(1)% Cu deficiency in the telluride layer when synthesized at high temperatures, corresponding to a Mn oxidation state of +2.18(2), and neutron powder diffraction revealed the presence of a sole highly asymmetric Warren-type magnetic peak, characteristic of magnetic ordering that is highly two-dimensional and not fully developed over a long range. Topotactic oxidation by the chemical deintercalation of further copper using a solution of I2 in acetonitrile offers control over the Mn oxidation state and, hence, the magnetic ordering: oxidation yielded Sr2MnO2Cu1.58(2)Te2 (Mn oxidation state of +2.42(2)) in which ferromagnetic interactions between Mn ions result from Mn2+/3+ mixed valence, resulting in a long-range-ordered A-type antiferromagnet with ferromagnetic MnO2 layers coupled antiferromagnetically.

Layered CeSO and LiCeSO Oxide Chalcogenides Obtained via Topotactic Oxidative and Reductive Transformations.

The chemical accessibility of the CeIV oxidation state enables redox chemistry to be performed on the naturally coinage-metal-deficient phases CeM1- xSO (M = Cu, Ag). A metastable black compound with the PbFCl structure type (space group P4/ nmm: a = 3.8396(1) Å, c = 6.607(4) Å, V = 97.40(6) Å3) and a composition approaching CeSO is obtained by deintercalation of Ag from CeAg0.8SO. High-resolution transmission electron microscopy reveals the presence of large defect-free regions in CeSO, but stacking faults are also evident which can be incorporated into a quantitative model to account for the severe peak anisotropy evident in all the high-resolution X-ray and neutron diffractograms of bulk CeSO samples; these suggest that a few percent of residual Ag remains. A straw-colored compound with the filled PbFCl (i.e., ZrSiCuAs- or HfCuSi2-type) structure (space group P4/ nmm: a = 3.98171(1) Å, c = 8.70913(5) Å, V = 138.075(1) Å3) and a composition close to LiCeSO, but with small amounts of residual Ag, is obtained by direct reductive lithiation of CeAg0.8SO or by insertion of Li into CeSO using chemical or electrochemical means. Computation of the band structure of pure, stoichiometric CeSO predicts it to be a Ce4+ compound with the 4f-states lying approximately 1 eV above the sulfide-dominated valence band maximum. Accordingly, the effective magnetic moment per Ce ion measured in the CeSO samples is much reduced from the value found for the Ce3+-containing LiCeSO, and the residual paramagnetism corresponds to the Ce3+ ions remaining due to the presence of residual Ag, which presumably reflects the difficulty of stabilizing Ce4+ in the presence of sulfide (S2-). Comparison of the behavior of CeCu0.8SO with that of CeAg0.8SO reveals much slower reaction kinetics associated with the Cu1- xS layers, and this enables intermediate CeCu1- xLi xSO phases to be isolated.

ELDOR-detected NMR beyond hyperfine couplings: a case study with Cu(ii)-porphyrin dimers.

The pulse EPR method ELDOR-detected NMR (EDNMR) is applied to two Cu(ii)-porphyrin dimers that are suitable building blocks for molecular wires. One of the dimers is meso-meso singly linked, the other one is ß, meso, ß-fused. We show experimentally and theoretically that EDNMR spectra contain information about the electron-electron couplings. The spectra of the singly linked dimer are consistent with a perpendicular arrangement of the porphyrin planes and negligible exchange coupling. In addition, the resolution is good enough to distinguish 63Cu and 65Cu in frozen glassy solution and to resolve a metal-ion nuclear quadrupole coupling of 32 MHz. In the case of the fused dimer, we observe so far unreported signal enhancements, or anti-holes, in the EDNMR spectra. These are readily explained in a generalized framework based on [Cox et al., J. Magn. Reson., 2017, 280, 63-78], if an effective spin of S = 1 is assumed, in accordance with SQUID measurements. The positions of the anti-holes encode a zero-field splitting with |D| = 240 MHz, which is about twice as large as expected from the point-dipole approximation. These findings demonstrate the previously unrecognized applicability and versatility of the EDNMR technique in the quantitative study of complex paramagnetic compounds.

In-situ Electrochemical X-ray Diffraction: A Rigorous Method to Navigate within Phase Diagrams Reveals ß-Fe1+x Se as Superconductor for All x.

We report the precise postsynthetic control of the composition of ß-Fe1+x Se by electrochemistry with simultaneous tracking of the associated structural changes via in situ synchrotron X-ray diffraction. We access the full phase width of 0.01

Synthesis, Structure, and Properties of the Layered Oxide Chalcogenides Sr2CuO2Cu2S2 and Sr2CuO2Cu2Se2.

The structures of two new oxide chalcogenide phases, Sr2CuO2Cu2S2 and Sr2CuO2Cu2Se2, are reported, both of which contain infinite CuO2 planes containing Cu2+ and which have Cu+ ions in the sulfide or selenide layers. Powder neutron diffraction measurements show that Sr2CuO2Cu2Se2 exhibits long-range magnetic ordering with a magnetic structure based on antiferromagnetic interactions between nearest-neighbor Cu2+ ions, leading to a √2 a × âˆš2 a × 2 c expansion of the nuclear cell. The ordered moment of 0.39(6) µB on the Cu2+ ions at 1.7 K is consistent with the value predicted by density functional theory calculations. The compounds are structurally related to the cuprate superconductors and may also be considered as analogues of the parent phases of this class of superconductor such as Sr2CuO2Cl2 or La2CuO4. In the present case, however, the top of the chalcogenide-based valence band is very close to the vacant Cu2+ 3d states of the conduction band, leading to relatively high measured conductivity.

Complex Magnetic Ordering in the Oxide Selenide Sr2Fe3Se2O3.

Sr2Fe3Se2O3 is a localized-moment iron oxide selenide in which two unusual coordinations for Fe2+ ions form two sublattices in a 2:1 ratio. In the paramagnetic region at room temperature, the compound adopts the crystal structure first reported for Sr2Co3S2O3, crystallizing in space group Pbam with a = 7.8121 Å, b = 10.2375 Å, c = 3.9939 Å, and Z = 2. The sublattice occupied by two-thirds of the iron ions (Fe2 site) is formed by a network of distorted mer-[FeSe3O3] octahedra linked via shared Se2 edges and O vertices forming layers, which connect to other layers by shared Se vertices. As shown by magnetometry, neutron powder diffraction, and Mössbauer spectroscopy measurements, these moments undergo long-range magnetic ordering below TN1 = 118 K, initially adopting a magnetic structure with a propagation vector (1/2 - δ, 0, 1/2) (0 ≤ δ ≤ 0.1) which is incommensurate with the nuclear structure and described in the Pbam1 '( a01/2)000 s magnetic superspace group, until at 92 K ( TINC) there is a first order lock-in transition to a structure in which these Fe2 moments form a magnetic structure with a propagation vector (1/2, 0, 1/2) which may be modeled using a 2 a × b × 2 c expansion of the nuclear cell in space group 36.178 B a b21 m (BNS notation). Below TN2 = 52 K the remaining third of the Fe2+ moments (Fe1 site) which are in a compressed trans-[FeSe4O2] octahedral environment undergo long-range ordering, as is evident from the magnetometry, the Mössbauer spectra, and the appearance of new magnetic Bragg peaks in the neutron diffractograms. The ordering of the second set of moments on the Fe1 sites results in a slight reorientation of the majority moments on the Fe2 sites. The magnetic structure at 1.5 K is described by a 2 a × 2 b × 2 c expansion of the nuclear cell in space group 9.40 I a b (BNS notation).

Crystal and Magnetic Structures of the Oxide Sulfides CaCoSO and BaCoSO.

CaCoSO, synthesized from CaO, Co, and S at 900 °C, is isostructural with CaZnSO and CaFeSO. The structure is non-centrosymmetric by virtue of the arrangement of the vertex-sharing CoS3O tetrahedra which are linked by their sulfide vertices to form layers. The crystal structure adopts space group P63mc (No. 186), and the lattice parameters are a = 3.7524(9) Å and c = 11.138(3) Å at room temperature with two formula units in the unit cell. The compound is highly insulating, and powder neutron diffraction measurements reveal long-range antiferromagnetic order with a propagation vector k = (1/3, 1/3, 1/2). The magnetic scattering from a powder sample can be modeled starting from a 120° arrangement of Co(2+) spin vectors in the triangular planes and then applying a canting out of the planes which can be modeled in the magnetic space group C(c)c (space group 9.40 in the Belov, Neronova, and Smirnova (BNS) scheme) with Co(2+) moments of 2.72(5) µ(B). The antiferromagnetic structure of the recently reported compound BaCoSO, which has a very different crystal structure from CaCoSO, is also described, and this magnetic structure and the magnitude of the ordered moment (2.75(2) µ(B)) are found by experiment to be similar to those predicted computationally.

Complex Microstructure and Magnetism in Polymorphic CaFeSeO.

The structural complexity of the antiferromagnetic oxide selenide CaFeSeO is described. The compound contains puckered FeSeO layers composed of FeSe2O2 tetrahedra sharing all their vertexes. Two polymorphs coexist that can be derived from an archetype BaZnSO structure by cooperative tilting of the FeSe2O2 tetrahedra. The polymorphs differ in the relative arrangement of the puckered layers of vertex-linked FeSe2O2 tetrahedra. In a noncentrosymmetric Cmc21 polymorph (a = 3.89684(2) Å, b = 13.22054(8) Å, c = 5.93625(2) Å) the layers are related by the C-centering translation, while in a centrosymmetric Pmcn polymorph, with a similar cell metric (a = 3.89557(6) Å, b = 13.2237(6) Å, c = 5.9363(3) Å), the layers are related by inversion. The compound shows long-range antiferromagnetic order below a Neél temperature of 159(1) K with both polymorphs showing antiferromagnetic coupling via Fe-O-Fe linkages and ferromagnetic coupling via Fe-Se-Fe linkages within the FeSeO layers. The magnetic susceptibility also shows evidence for weak ferromagnetism which is modeled in the refinements of the magnetic structure as arising from an uncompensated spin canting in the noncentrosymmetric polymorph. There is also a spin glass component to the magnetism which likely arises from the disordered regions of the structure evident in the transmission electron microscopy.

The Parent Li(OH)FeSe Phase of Lithium Iron Hydroxide Selenide Superconductors.

Lithiation of hydrothermally synthesized Li1-xFex(OH)Fe1-ySe turns on high-temperature superconductivity when iron ions are displaced from the hydroxide layers by reductive lithiation to fill the vacancies in the iron selenide layers. Further lithiation results in reductive iron extrusion from the hydroxide layers, which turns off superconductivity again as the stoichiometric composition Li(OH)FeSe is approached. The results demonstrate the twin requirements of stoichiometric FeSe layers and reduction of Fe below the +2 oxidation state as found in several iron selenide superconductors.

Spin-reorientation transition in CeMnAsO.

High-resolution X-ray and neutron powder diffraction are used to reveal details of the spin-reorientation transition in the layered oxide pnictide CeMnAsO. Above 38 K, the localized moments on Mn(2+) are antiferromagnetically ordered in a checkerboard fashion within the antifluorite-type MnAs planes and are oriented perpendicular to the planes. Below 38 K, reorientation of these moments into the planes commences. This is complete by 34 K and is coincident with long-range ordering of the Ce(3+) moments. The Ce(3+) and Mn(2+) moments have an arrangement that is different in detail from that in the isostructural NdMnAsO and PrMnSbO. There is no evidence for structural distortion, as found for PrMnSbO and related Pr(3+)-containing compounds, although there is evidence for a very slight (0.025%) misfit between the magnetic and structural cells below the spin-reorientation transition. It is clarified that neutron powder diffraction methods are unable to distinguish between collinear and noncollinear arrangements of manganese and lanthanide moments when the moments have a component parallel to the MnAs planes. A proposal from computational analysis that NdMnAsO and CeMnAsO should adopt different magnetic structures on the basis of the different balances between biquadratic and antisymmetric exchange interactions should be tested using alternative methods.

Soft chemical control of superconductivity in lithium iron selenide hydroxides Li(1-x)Fe(x)(OH)Fe(1-y)Se.

Hydrothermal synthesis is described of layered lithium iron selenide hydroxides Li(1-x)Fe(x)(OH)Fe(1-y)Se (x ∼ 0.2; 0.02 < y < 0.15) with a wide range of iron site vacancy concentrations in the iron selenide layers. This iron vacancy concentration is revealed as the only significant compositional variable and as the key parameter controlling the crystal structure and the electronic properties. Single crystal X-ray diffraction, neutron powder diffraction, and X-ray absorption spectroscopy measurements are used to demonstrate that superconductivity at temperatures as high as 40 K is observed in the hydrothermally synthesized samples when the iron vacancy concentration is low (y < 0.05) and when the iron oxidation state is reduced slightly below +2, while samples with a higher vacancy concentration and a correspondingly higher iron oxidation state are not superconducting. The importance of combining a low iron oxidation state with a low vacancy concentration in the iron selenide layers is emphasized by the demonstration that reductive postsynthetic lithiation of the samples turns on superconductivity with critical temperatures exceeding 40 K by displacing iron atoms from the Li(1-x)Fe(x)(OH) reservoir layer to fill vacancies in the selenide layer.

Zero-strain reductive intercalation in a molecular framework.

Reductive intercalation of potassium within the molecular framework Ag3[Fe(CN)6] gives rise to a volume strain that is an order of magnitude smaller than is typical for common ion-storage materials. We suggest that framework flexibility might be exploited as a general strategy for reducing cycling strain in battery and ion-storage materials.

Ammonia-rich high-temperature superconducting intercalates of iron selenide revealed through time-resolved in situ X-ray and neutron diffraction.

The development of a technique for following in situ the reactions of solids with alkali metal/ammonia solutions, using time-resolved X-ray diffraction methods, reveals high-temperature superconducting ammonia-rich intercalates of iron selenide which reversibly absorb and desorb ammonia around ambient temperatures.

Enhancement of the superconducting transition temperature of FeSe by intercalation of a molecular spacer layer.

The discovery of high-temperature superconductivity in a layered iron arsenide has led to an intensive search to optimize the superconducting properties of iron-based superconductors by changing the chemical composition of the spacer layer between adjacent anionic iron arsenide layers. Superconductivity has been found in iron arsenides with cationic spacer layers consisting of metal ions (for example, Li(+), Na(+), K(+), Ba(2+)) or PbO- or perovskite-type oxide layers, and also in Fe(1.01)Se (ref. 8) with neutral layers similar in structure to those found in the iron arsenides and no spacer layer. Here we demonstrate the synthesis of Li(x)(NH(2))(y)(NH(3))(1-y)Fe(2)Se(2) (x~0.6; y~0.2), with lithium ions, lithium amide and ammonia acting as the spacer layer between FeSe layers, which exhibits superconductivity at 43(1) K, higher than in any FeSe-derived compound reported so far. We have determined the crystal structure using neutron powder diffraction and used magnetometry and muon-spin rotation data to determine the superconducting properties. This new synthetic route opens up the possibility of further exploitation of related molecular intercalations in this and other systems to greatly optimize the superconducting properties in this family.

Anionic Redox Topochemistry for Materials Design: Chalcogenides and Beyond.

Topochemistry refers to a generic category of solid-state reactions in which precursors and products display strong filiation in their crystal structures. Various low-dimensional materials are subject to this stepwise structure transformation by accommodating guest atoms or molecules in between their 2D slabs or 1D chains loosely bound by van der Waals (vdW) interactions. Those processes are driven by redox reactions between guests and the host framework, where transition metal cations have been widely exploited as the redox center. Topochemistry coupled with this cationic redox not only enables technological applications such as Li-ion secondary batteries but also serves as a powerful tool for structural or electronic fine-tuning of layered transition metal compounds. Over recent years, we have been pursuing materials design beyond this cationic redox topochemistry that was mostly limited to 2D or 1D vdW systems. For this, we proposed new topochemical reactions of non-vdW compounds built of 2D arrays of anionic chalcogen dimers alternating with redox-inert host cationic layers. These chalcogen dimers were found to undergo redox reaction with external metal elements, triggering either (1) insertion of these metals to construct 2D metal chalcogenides or (2) deintercalation of the constituent chalcogen anions. As a whole, this topochemistry works like a "zipper", where reductive cleavage of anionic chalcogen-chalcogen bonds opens up spaces in non-vdW materials, allowing the formation of novel layered structures. This Perspective briefly summarizes seminal examples of unique structure transformations achieved by anionic redox topochemistry as well as challenges on their syntheses and characterizations.

Sr2MnO2Na1.6Se2: A Metamagnetic Layered Oxychalcogenide Synthesized by Reductive Na Intercalation to Break [Se2]2- Perselenide Dimer Units.

Recent advances in anion-redox topochemistry have enabled the synthesis of metastable mixed-anion solids. Synthesis of the new transition metal oxychalcogenide Sr2MnO2Na1.6Se2 by topochemical Na intercalation into Sr2MnO2Se2 is reported here. Na intercalation is enabled by the redox activity of [Se2]2- perselenide dimers, where the Se-Se bonds are cleaved and a [Na2-x Se2](2+x)- antifluorite layer is formed. Freshly prepared samples have 16(1) % Na-site vacancies corresponding to a formal oxidation state of Mn of +2.32, a mixed-valence between Mn2+ (d5) and Mn3+ (d4). Samples are highly prone to deintercalation of Na, and over two years, even in an argon glovebox environment, the Na content decreased by 4(1) %, leading to slight oxidation of Mn and a significantly increased long-range ordered moment on the Mn site as measured using neutron powder diffraction. The magnetic structure derived from neutron powder diffraction at 5 K reveals that the compound orders magnetically with ferromagnetic MnO2 sheets coupled antiferromagnetically. The aged sample shows a metamagnetic transition from bulk antiferromagnetic to ferromagnetic behavior in an applied magnetic field of 2 T, in contrast to the Cu analogue, Sr2MnO2Cu1.55Se2, where there is only a hint that such a transition may occur at fields exceeding 7 T. This is presumably due to the higher ionic character of [Na2-x Se2](2+x)- layers compared to [Cu2-x Se2](2+x)- layers, reducing the strength of the antiferromagnetic interactions between MnO2 sheets. Electrochemical Na intercalation into Sr2MnO2Se2 leads to the formation of multiphase sodiated products. The work shows the potential of anion redox to yield novel compounds with intriguing physical properties.