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DOE OSTI2020

Materials Data on K2Pd(S4O13)2 by Materials Project

K2Pd(S4O13)2 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. K1+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of K–O bond distances ranging from 2.87–3.27 Å. Pd2+ is bonded in a square co-planar geometry to four O2- atoms. There are two shorter (2.04 Å) and two longer (2.07 Å) Pd–O bond lengths. There are four inequivalent S6+ sites. In the first S6+ site, S6+ is bonded to four O2- atoms to form corner-sharing SO4 tetrahedra. There are a spread of S–O bond distances ranging from 1.43–1.75 Å. In the second S6+ site, S6+ is bonded to four O2- atoms to form corner-sharing SO4 tetrahedra. There are a spread of S–O bond distances ranging from 1.42–1.65 Å. In the third S6+ site, S6+ is bonded to four O2- atoms to form corner-sharing SO4 tetrahedra. There are a spread of S–O bond distances ranging from 1.43–1.80 Å. In the fourth S6+ site, S6+ is bonded to four O2- atoms to form corner-sharing SO4 tetrahedra. There are a spread of S–O bond distances ranging from 1.42–1.65 Å. There are thirteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the second O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the third O2- site, O2- is bonded in a bent 120 degrees geometry to two S6+ atoms. In the fourth O2- site, O2- is bonded in a bent 120 degrees geometry to one Pd2+ and one S6+ atom. In the fifth O2- site, O2- is bonded in a single-bond geometry to two equivalent K1+ and one S6+ atom. In the sixth O2- site, O2- is bonded in a bent 120 degrees geometry to two S6+ atoms. In the seventh O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the eighth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the ninth O2- site, O2- is bonded in a single-bond geometry to one K1+ and one S6+ atom. In the tenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Pd2+ and one S6+ atom. In the eleventh O2- site, O2- is bonded in a bent 120 degrees geometry to two S6+ atoms. In the twelfth O2- site, O2- is bonded in a single-bond geometry to one K1+ and one S6+ atom. In the thirteenth O2- site, O2- is bonded in a single-bond geometry to one K1+ and one S6+ atom.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Materials Data on Li2Pd(N2O5)2 by Materials Project

Li2N3O8PdNO2 crystallizes in the orthorhombic Pna2_1 space group. The structure is one-dimensional and consists of four nitrous acid molecules; four palladium on carbon molecules; and two Li2N3O8 ribbons oriented in the (1, 0, 0) direction. In each Li2N3O8 ribbon, there are two inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Li–O bond distances ranging from 1.95–2.36 Å. In the second Li1+ site, Li1+ is bonded in a distorted square pyramidal geometry to five O2- atoms. There are a spread of Li–O bond distances ranging from 1.97–2.25 Å. There are three inequivalent N4+ sites. In the first N4+ site, N4+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.24 Å) and one longer (1.25 Å) N–O bond length. In the second N4+ site, N4+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.23 Å) and one longer (1.25 Å) N–O bond length. In the third N4+ site, N4+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.23 Å) and one longer (1.25 Å) N–O bond length. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two Li1+ atoms. In the second O2- site, O2- is bonded in a bent 150 degrees geometry to one Li1+ and one N4+ atom. In the third O2- site, O2- is bonded in a bent 120 degrees geometry to one Li1+ and one N4+ atom. In the fourth O2- site, O2- is bonded in a water-like geometry to two Li1+ atoms. In the fifth O2- site, O2- is bonded in a 1-coordinate geometry to two Li1+ and one N4+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to two Li1+ and one N4+ atom. In the seventh O2- site, O2- is bonded in a single-bond geometry to one N4+ atom. In the eighth O2- site, O2- is bonded in a single-bond geometry to one N4+ atom.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Materials Data on Na6H2Pd(S2O7)2 by Materials Project

Pd(Na3HS2O7)2 crystallizes in the tetragonal I4_1/a space group. The structure is three-dimensional and consists of eight palladium molecules and one Na3HS2O7 framework. In the Na3HS2O7 framework, there are three inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded to six O2- atoms to form distorted edge-sharing NaO6 pentagonal pyramids. There are a spread of Na–O bond distances ranging from 2.41–2.78 Å. In the second Na1+ site, Na1+ is bonded in a 5-coordinate geometry to six O2- atoms. There are a spread of Na–O bond distances ranging from 2.37–2.94 Å. In the third Na1+ site, Na1+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Na–O bond distances ranging from 2.32–2.53 Å. H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. There are two inequivalent S4+ sites. In the first S4+ site, S4+ is bonded in a trigonal non-coplanar geometry to three O2- atoms. There are a spread of S–O bond distances ranging from 1.49–1.51 Å. In the second S4+ site, S4+ is bonded in a trigonal non-coplanar geometry to three O2- atoms. There are a spread of S–O bond distances ranging from 1.49–1.51 Å. There are seven inequivalent O2- sites. In the first O2- site, O2- is bonded in a 1-coordinate geometry to three Na1+ and one S4+ atom. In the second O2- site, O2- is bonded in a 4-coordinate geometry to three Na1+ and one S4+ atom. In the third O2- site, O2- is bonded in a 3-coordinate geometry to two Na1+ and one S4+ atom. In the fourth O2- site, O2- is bonded in a distorted trigonal pyramidal geometry to three Na1+ and one S4+ atom. In the fifth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Na1+ and one S4+ atom. In the sixth O2- site, O2- is bonded in a distorted T-shaped geometry to two Na1+ and one S4+ atom. In the seventh O2- site, O2- is bonded in a distorted single-bond geometry to one Na1+ and one H1+ atom.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Materials Data on K2Pd(NO3)4 by Materials Project

K2Pd(NO3)4 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. there are two inequivalent K1+ sites. In the first K1+ site, K1+ is bonded in a 7-coordinate geometry to ten O2- atoms. There are a spread of K–O bond distances ranging from 2.81–3.37 Å. In the second K1+ site, K1+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of K–O bond distances ranging from 2.92–3.20 Å. Pd2+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are two shorter (2.03 Å) and two longer (2.04 Å) Pd–O bond lengths. There are four inequivalent N5+ sites. In the first N5+ site, N5+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of N–O bond distances ranging from 1.24–1.33 Å. In the second N5+ site, N5+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of N–O bond distances ranging from 1.24–1.33 Å. In the third N5+ site, N5+ is bonded in a trigonal planar geometry to three O2- atoms. There is two shorter (1.24 Å) and one longer (1.33 Å) N–O bond length. In the fourth N5+ site, N5+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of N–O bond distances ranging from 1.24–1.33 Å. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to two K1+ and one N5+ atom. In the second O2- site, O2- is bonded in a 3-coordinate geometry to one K1+, one Pd2+, and one N5+ atom. In the third O2- site, O2- is bonded in a 2-coordinate geometry to one K1+, one Pd2+, and one N5+ atom. In the fourth O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent K1+ and one N5+ atom. In the fifth O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent K1+ and one N5+ atom. In the sixth O2- site, O2- is bonded in a 2-coordinate geometry to one K1+, one Pd2+, and one N5+ atom. In the seventh O2- site, O2- is bonded in a 2-coordinate geometry to one K1+, one Pd2+, and one N5+ atom. In the eighth O2- site, O2- is bonded in a distorted single-bond geometry to two K1+ and one N5+ atom. In the ninth O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent K1+ and one N5+ atom. In the tenth O2- site, O2- is bonded in a distorted single-bond geometry to two K1+ and one N5+ atom. In the eleventh O2- site, O2- is bonded in a distorted single-bond geometry to two K1+ and one N5+ atom. In the twelfth O2- site, O2- is bonded in a distorted single-bond geometry to two K1+ and one N5+ atom.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Minimizing the diffusivity difference between vacancies and interstitials in multi-principal element alloys

Interstitial atoms usually diffuse much faster than vacancies, which is often the root cause for the ineffective recombination of point defects in metals under irradiation. Here, via ab initio modeling of single-defect diffusion behavior in the equiatomic NiCoCrFe(Pd) alloy, we demonstrate an alloy design strategy that can reduce the diffusivity difference between the two types of point defects. The two diffusivities become almost equal after substituting the NiCoCrFe base alloy with Pd. The underlying mechanism is that Pd, with a much larger atomic size (hence larger compressibility) than the rest of the constituents, not only heightens the activation energy barrier ( E a ) for interstitial motion by narrowing the diffusion channels but simultaneously also reduces E a for vacancies due to less energy penalty required for bond length change between the initial and the saddle states. Our findings have a broad implication that the dynamics of point defects can be manipulated by taking advantage of the atomic size disparity, to facilitate point-defect annihilation that suppresses void formation and swelling, thereby improving radiation tolerance.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Materials Data on K2Pd(NO2)4 by Materials Project

K2Pd(NO2)4 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. there are two inequivalent K1+ sites. In the first K1+ site, K1+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of K–O bond distances ranging from 2.74–3.36 Å. In the second K1+ site, K1+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of K–O bond distances ranging from 2.82–3.22 Å. There are two inequivalent Pd2+ sites. In the first Pd2+ site, Pd2+ is bonded in a distorted square co-planar geometry to four N3+ atoms. There are two shorter (2.05 Å) and two longer (2.08 Å) Pd–N bond lengths. In the second Pd2+ site, Pd2+ is bonded in a distorted square co-planar geometry to four N3+ atoms. All Pd–N bond lengths are 2.06 Å. There are four inequivalent N3+ sites. In the first N3+ site, N3+ is bonded in a bent 120 degrees geometry to one Pd2+ and two O2- atoms. Both N–O bond lengths are 1.25 Å. In the second N3+ site, N3+ is bonded in a distorted bent 120 degrees geometry to one Pd2+ and two O2- atoms. There is one shorter (1.25 Å) and one longer (1.26 Å) N–O bond length. In the third N3+ site, N3+ is bonded in a bent 120 degrees geometry to one Pd2+ and two O2- atoms. Both N–O bond lengths are 1.25 Å. In the fourth N3+ site, N3+ is bonded in a bent 120 degrees geometry to one Pd2+ and two O2- atoms. Both N–O bond lengths are 1.25 Å. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to three K1+ and one N3+ atom. In the second O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent K1+ and one N3+ atom. In the third O2- site, O2- is bonded in a 1-coordinate geometry to two K1+ and one N3+ atom. In the fourth O2- site, O2- is bonded in a 1-coordinate geometry to two equivalent K1+ and one N3+ atom. In the fifth O2- site, O2- is bonded in a distorted single-bond geometry to two K1+ and one N3+ atom. In the sixth O2- site, O2- is bonded in a 1-coordinate geometry to two equivalent K1+ and one N3+ atom. In the seventh O2- site, O2- is bonded in a distorted single-bond geometry to two K1+ and one N3+ atom. In the eighth O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent K1+ and one N3+ atom.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Tuning spin–orbit coupling in (6,5) single-walled carbon nanotube doped with sp 3 defects

Single-walled carbon nanotubes (SWCNTs) containing sp 3 defects are a promising class of optoelectronic materials with bright photoluminescence and demonstrated single-photon emission. Using density functional theory simulations, complemented by measurements, we investigate the electronic structure of a series of quantum defects attached to (6,5) SWCNT with the goal of tuning the spin–orbit coupling by introduction of a heavy atom in the defect structure. We characterize the ground state electronic and spin properties of four synthesized and three potential defects on the tube and find that all of the synthesized defects considered introduce a localized midgap defect-centered state containing a single electron, ≈0.2–0.3 eV above the valence band. The spin density is located at the sp 3 defect site with negligible spin–orbit coupling even with the presence of a Pd atom. Three additional functional groups were tested via computation to increase spin localization near the metal, thereby increasing spin–orbit coupling. We predict that only the chlorodiphosphanepalladium(II)– [Cl(PH 3 ) 2 Pd(II)–] defect results in increased spin–orbit splitting of the defect state and the conduction band associated with the pristine-like SWCNT, a measure of the spin–orbit coupling of excited state transitions. This study suggests that for unpassivated sp 3 defects in (6,5) SWCNT, forming a direct bond between a heavy atom and the sp 3 carbon allows for tuning of spin–orbit coupling.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2020

In Situ Dispersion of Palladium on TiO 2 During Reverse Water–Gas Shift Reaction: Formation of Atomically Dispersed Palladium

The application of single-atom catalysts (SACs) to high-temperature hydrogenation requires materials that thermodynamically favor metal atom isolation over cluster formation. Here, we show that Pd can be predominantly dispersed as isolated atoms onto TiO 2 during the reverse water-gas shift (rWGS) reaction at 400 °C. Achieving atomic dispersion requires an artificial increase of the absolute TiO 2 surface area by an order of magnitude and can be accomplished by physically mixing a precatalyst (Pd/TiO 2 ) with neat TiO 2 prior to the rWGS reaction. Furthermore, the in situ dispersion of Pd was reflected through a continuous increase of rWGS activity over 92 h and supported by kinetic analysis, infrared and X-ray absorption spectroscopies and scanning transmission electron microscopy. The thermodynamic stability of Pd under high-temperature rWGS conditions is associated with Pd-Ti coordination, which manifests upon O-vacancy formation and the artificial increase in TiO 2 surface area.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Materials Data on K2Pd(S2O7)3 by Materials Project

K2Pd(S2O7)3 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are four inequivalent K1+ sites. In the first K1+ site, K1+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of K–O bond distances ranging from 2.83–3.21 Å. In the second K1+ site, K1+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of K–O bond distances ranging from 2.81–3.31 Å. In the third K1+ site, K1+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of K–O bond distances ranging from 2.81–3.12 Å. In the fourth K1+ site, K1+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of K–O bond distances ranging from 2.83–3.08 Å. There are two inequivalent Pd4+ sites. In the first Pd4+ site, Pd4+ is bonded to six O2- atoms to form PdO6 octahedra that share corners with six SO4 tetrahedra. There are a spread of Pd–O bond distances ranging from 2.03–2.05 Å. In the second Pd4+ site, Pd4+ is bonded to six O2- atoms to form PdO6 octahedra that share corners with six SO4 tetrahedra. There are a spread of Pd–O bond distances ranging from 2.03–2.05 Å. There are twelve inequivalent S6+ sites. In the first S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share a cornercorner with one PdO6 octahedra and a cornercorner with one SO4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. There are a spread of S–O bond distances ranging from 1.43–1.68 Å. In the second S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share a cornercorner with one PdO6 octahedra and a cornercorner with one SO4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. There are a spread of S–O bond distances ranging from 1.43–1.68 Å. In the third S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share a cornercorner with one PdO6 octahedra and a cornercorner with one SO4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. There are a spread of S–O bond distances ranging from 1.43–1.66 Å. In the fourth S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share a cornercorner with one PdO6 octahedra and a cornercorner with one SO4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. There are a spread of S–O bond distances ranging from 1.43–1.66 Å. In the fifth S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share a cornercorner with one PdO6 octahedra and a cornercorner with one SO4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. There are a spread of S–O bond distances ranging from 1.43–1.66 Å. In the sixth S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share a cornercorner with one PdO6 octahedra and a cornercorner with one SO4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. There are a spread of S–O bond distances ranging from 1.43–1.66 Å. In the seventh S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share a cornercorner with one PdO6 octahedra and a cornercorner with one SO4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. There are a spread of S–O bond distances ranging from 1.43–1.66 Å. In the eighth S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share a cornercorner with one PdO6 octahedra and a cornercorner with one SO4 tetrahedra. The corner-sharing octahedral tilt angles are 57°. There are a spread of S–O bond distances ranging from 1.43–1.66 Å. In the ninth S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share a cornercorner with one PdO6 octahedra and a cornercorner with one SO4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. There are a spread of S–O bond distances ranging from 1.43–1.66 Å. In the tenth S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share a cornercorner with one PdO6 octahedra and a cornercorner with one SO4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. There are a spread of S–O bond distances ranging from 1.43–1.68 Å. In the eleventh S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share a cornercorner with one PdO6 octahedra and a cornercorner with one SO4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. There are a spread of S–O bond distances ranging from 1.43–1.67 Å. In the twelfth S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share a cornercorner with one PdO6 octahedra and a cornercorner with one SO4 tetrahedra. The corner-sharing octahedral tilt angles are 57°. There are a spread of S–O bond distances ranging from 1.43–1.67 Å. There are forty-two inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 120 degrees geometry to one Pd4+ and one S6+ atom. In the second O2- site, O2- is bonded in a bent 120 degrees geometry to one Pd4+ and one S6+ atom. In the third O2- site, O2- is bonded in a bent 120 degrees geometry to one Pd4+ and one S6+ atom. In the fourth O2- site, O2- is bonded in a bent 120 degrees geometry to one Pd4+ and one S6+ atom. In the fifth O2- site, O2- is bonded in a bent 120 degrees geometry to one Pd4+ and one S6+ atom. In the sixth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the seventh O2- site, O2- is bonded in a bent 120 degrees geometry to one Pd4+ and one S6+ atom. In the eighth O2- site, O2- is bonded in a bent 120 degrees geometry to one K1+ and two S6+ atoms. In the ninth O2- site, O2- is bonded in a bent 120 degrees geometry to one Pd4+ and one S6+ atom. In the tenth O2- site, O2- is bonded in a bent 120 degrees geometry to one Pd4+ and one S6+ atom. In the eleventh O2- site, O2- is bonded in a bent 120 degrees geometry to one Pd4+ and one S6+ atom. In the twelfth O2- site, O2- is bonded in a bent 120 degrees geometry to two S6+ atoms. In the thirteenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one K1+ and two S6+ atoms. In the fourteenth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the fifteenth O2- site, O2- is bonded in a bent 120 degrees geometry to one Pd4+ and one S6+ atom. In the sixteenth O2- site, O2- is bonded in a bent 120 degrees geometry to one Pd4+ and one S6+ atom. In the seventeenth O2- site, O2- is bonded in a bent 120 degrees geometry to two S6+ atoms. In the eighteenth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the nineteenth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the twentieth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the twenty-first O2- site, O2- is bonded in a distorted single-bond geometry to two K1+ and one S6+ atom. In the twenty-second O2- site, O2- is bonded in a distorted single-bond geometry to two K1+ and one S6+ atom. In the twenty-third O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the twenty-fourth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the twenty-fifth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the twenty-sixth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the twenty-seventh O2- site, O2- is bonded in a bent 120 degrees geometry to one K1+ and two S6+ atoms. In the twenty-eighth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the twenty-ninth O2- site, O2- is bonded in a single-bond geometry to one K1+ and one S6+ atom. In the thirtieth O2- site, O2- is bonded in a bent 120 degrees geometry to one Pd4+ and one S6+ atom. In the thirty-first O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the thirty-second O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the thirty-third O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the thirty-fourth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the thirty-fifth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the thirty-sixth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the thirty-seventh O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom. In the thirty-eighth O2- site, O2- is bonded in a bent 120 degrees geometry to one K1+ and two S6+ atoms. In the thirty-ninth O2- site, O2- is bonded in a distorted single-bond geometry to two K1+ and one S6+ atom. In the fortieth O2- site, O2- is bonded in a distorted single-bond geometry to two K1+ and one S6+ atom. In the forty-first O2- site, O2- is bonded in a single-bond geometry to one K1+ and one S6+ atom. In the forty-second O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one S6+ atom.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Materials Data on Na2Pd(NO3)4 by Materials Project

Na2Pd(NO3)4 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. Na1+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of Na–O bond distances ranging from 2.44–2.92 Å. Pd2+ is bonded in a square co-planar geometry to four O2- atoms. All Pd–O bond lengths are 2.04 Å. There are two inequivalent N5+ sites. In the first N5+ site, N5+ is bonded in a trigonal planar geometry to three O2- atoms. There is two shorter (1.24 Å) and one longer (1.33 Å) N–O bond length. In the second N5+ site, N5+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of N–O bond distances ranging from 1.24–1.32 Å. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal planar geometry to one Na1+, one Pd2+, and one N5+ atom. In the second O2- site, O2- is bonded in a bent 150 degrees geometry to one Na1+ and one N5+ atom. In the third O2- site, O2- is bonded in a 2-coordinate geometry to one Na1+ and one N5+ atom. In the fourth O2- site, O2- is bonded in a bent 120 degrees geometry to one Pd2+ and one N5+ atom. In the fifth O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Na1+ and one N5+ atom. In the sixth O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent Na1+ and one N5+ atom.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Materials Data on H4Pd(NO4)2 by Materials Project

PdH4(NO4)2 crystallizes in the orthorhombic Pbca space group. The structure is zero-dimensional and consists of four akos015951075 molecules. Pd2+ is bonded in a square co-planar geometry to four O2- atoms. There are two shorter (2.03 Å) and two longer (2.07 Å) Pd–O bond lengths. N5+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of N–O bond distances ranging from 1.23–1.34 Å. There are two inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the second H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 1.00 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 120 degrees geometry to one Pd2+ and one N5+ atom. In the second O2- site, O2- is bonded in a single-bond geometry to one N5+ atom. In the third O2- site, O2- is bonded in a single-bond geometry to one N5+ atom. In the fourth O2- site, O2- is bonded in a distorted water-like geometry to one Pd2+ and two H1+ atoms.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Materials Data on KNa4Te2PdO22 by Materials Project

KNa4PdTe2O22 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. K is bonded in a 6-coordinate geometry to six O atoms. There are a spread of K–O bond distances ranging from 2.59–2.97 Å. There are four inequivalent Na sites. In the first Na site, Na is bonded in a 5-coordinate geometry to five O atoms. There are a spread of Na–O bond distances ranging from 2.20–2.66 Å. In the second Na site, Na is bonded in a 5-coordinate geometry to five O atoms. There are a spread of Na–O bond distances ranging from 2.36–2.57 Å. In the third Na site, Na is bonded in a 4-coordinate geometry to six O atoms. There are a spread of Na–O bond distances ranging from 2.21–2.98 Å. In the fourth Na site, Na is bonded in a 6-coordinate geometry to six O atoms. There are a spread of Na–O bond distances ranging from 2.32–2.87 Å. Pd is bonded to six O atoms to form PdO6 octahedra that share an edgeedge with one PdO6 octahedra, edges with two equivalent TeO6 octahedra, and an edgeedge with one TeO6 trigonal bipyramid. There are a spread of Pd–O bond distances ranging from 1.99–2.07 Å. There are two inequivalent Te sites. In the first Te site, Te is bonded to six O atoms to form distorted TeO6 trigonal bipyramids that share an edgeedge with one PdO6 octahedra. There are a spread of Te–O bond distances ranging from 1.90–2.66 Å. In the second Te site, Te is bonded to six O atoms to form distorted TeO6 octahedra that share edges with two equivalent PdO6 octahedra. There are a spread of Te–O bond distances ranging from 1.85–2.21 Å. There are twenty-two inequivalent O sites. In the first O site, O is bonded in an L-shaped geometry to one Na and one Te atom. In the second O site, O is bonded in a distorted bent 120 degrees geometry to one Te and one O atom. The O–O bond length is 1.26 Å. In the third O site, O is bonded in a single-bond geometry to one Te atom. In the fourth O site, O is bonded in a distorted trigonal planar geometry to two Na and one Te atom. In the fifth O site, O is bonded to one K, one Na, one Pd, and one Te atom to form distorted OKNaTePd trigonal pyramids that share a cornercorner with one ONa2TePd trigonal pyramid, an edgeedge with one OKNa2Te tetrahedra, and edges with two ONa2TePd trigonal pyramids. In the sixth O site, O is bonded to two Na, one Pd, and one Te atom to form distorted ONa2TePd trigonal pyramids that share a cornercorner with one OKNaTePd trigonal pyramid, an edgeedge with one OKNa2Te tetrahedra, and edges with two OKNaTePd trigonal pyramids. In the seventh O site, O is bonded to one K, one Na, one Pd, and one Te atom to form distorted OKNaTePd trigonal pyramids that share a cornercorner with one OKNa2Te tetrahedra, an edgeedge with one OKNa2Te tetrahedra, and edges with two OKNaTePd trigonal pyramids. In the eighth O site, O is bonded in a 4-coordinate geometry to one Na, two equivalent Pd, and one Te atom. In the ninth O site, O is bonded in a water-like geometry to one Pd and one Te atom. In the tenth O site, O is bonded to one K, two Na, and one Te atom to form a mixture of distorted edge and corner-sharing OKNa2Te tetrahedra. In the eleventh O site, O is bonded in a linear geometry to one Na and one Te atom. In the twelfth O site, O is bonded in a bent 150 degrees geometry to one Na and one Te atom. In the thirteenth O site, O is bonded in a 2-coordinate geometry to two Na and one O atom. The O–O bond length is 1.24 Å. In the fourteenth O site, O is bonded in a distorted T-shaped geometry to two Na and one O atom. The O–O bond length is 1.25 Å. In the fifteenth O site, O is bonded in a bent 120 degrees geometry to one Na and one O atom. The O–O bond length is 1.25 Å. In the sixteenth O site, O is bonded in a 2-coordinate geometry to two Na and one O atom. The O–O bond length is 1.25 Å. In the seventeenth O site, O is bonded in a single-bond geometry to one O atom. In the eighteenth O site, O is bonded in a water-like geometry to one K and one Na atom. In the nineteenth O site, O is bonded in a distorted bent 120 degrees geometry to one Na and one O atom. In the twentieth O site, O is bonded in a distorted linear geometry to one K and one O atom. In the twenty-first O site, O is bonded in a bent 150 degrees geometry to one Na and one O atom. In the twenty-second O site, O is bonded in a distorted bent 150 degrees geometry to one K and one O atom.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Materials Data on Cs2K2Pd2N8O25 by Materials Project

Cs2K2Pd2N8O25 crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. Cs1+ is bonded in a 12-coordinate geometry to twelve O2- atoms. There are a spread of Cs–O bond distances ranging from 3.26–3.64 Å. K1+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of K–O bond distances ranging from 2.84–2.99 Å. Pd3+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are two shorter (2.03 Å) and two longer (2.04 Å) Pd–O bond lengths. There are four inequivalent N5+ sites. In the first N5+ site, N5+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of N–O bond distances ranging from 1.24–1.33 Å. In the second N5+ site, N5+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of N–O bond distances ranging from 1.23–1.35 Å. In the third N5+ site, N5+ is bonded in a trigonal planar geometry to three O2- atoms. There is two shorter (1.24 Å) and one longer (1.34 Å) N–O bond length. In the fourth N5+ site, N5+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of N–O bond distances ranging from 1.23–1.34 Å. There are thirteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to one Cs1+ and one N5+ atom. In the second O2- site, O2- is bonded in a single-bond geometry to one Cs1+ and one N5+ atom. In the third O2- site, O2- is bonded in a 2-coordinate geometry to one K1+, one Pd3+, and one N5+ atom. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to one K1+, one Pd3+, and one N5+ atom. In the fifth O2- site, O2- is bonded in a single-bond geometry to two equivalent Cs1+ and one N5+ atom. In the sixth O2- site, O2- is bonded in a water-like geometry to two equivalent K1+ atoms. In the seventh O2- site, O2- is bonded in a single-bond geometry to one Cs1+, one K1+, and one N5+ atom. In the eighth O2- site, O2- is bonded in a single-bond geometry to two equivalent Cs1+ and one N5+ atom. In the ninth O2- site, O2- is bonded in a single-bond geometry to two equivalent Cs1+ and one N5+ atom. In the tenth O2- site, O2- is bonded in a 2-coordinate geometry to one K1+, one Pd3+, and one N5+ atom. In the eleventh O2- site, O2- is bonded in a single-bond geometry to two equivalent Cs1+ and one N5+ atom. In the twelfth O2- site, O2- is bonded in a 3-coordinate geometry to one K1+, one Pd3+, and one N5+ atom. In the thirteenth O2- site, O2- is bonded in a distorted single-bond geometry to one Cs1+, one K1+, and one N5+ atom.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Materials Data on CsPdCl3 by Materials Project

CsPdCl3 crystallizes in the orthorhombic Ibam space group. The structure is three-dimensional. Cs1+ is bonded in a 10-coordinate geometry to ten Cl1- atoms. There are a spread of Cs–Cl bond distances ranging from 3.66–3.91 Å. Pd2+ is bonded in a rectangular see-saw-like geometry to four Cl1- atoms. There are a spread of Pd–Cl bond distances ranging from 2.30–2.35 Å. There are three inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a distorted L-shaped geometry to two equivalent Cs1+ and two equivalent Pd2+ atoms. In the second Cl1- site, Cl1- is bonded in a distorted single-bond geometry to four equivalent Cs1+ and one Pd2+ atom. In the third Cl1- site, Cl1- is bonded in a 1-coordinate geometry to four equivalent Cs1+ and one Pd2+ atom.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Nitrogen Atom Transfer Catalysis by Metallonitrene C−H Insertion: Photocatalytic Amidation of Aldehydes

Abstract C−H amination and amidation by catalytic nitrene transfer are well‐established and typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion of (formal) terminal nitride ligands into C−H bonds is much less developed and catalytic nitrogen atom transfer remains unknown. We here report the synthesis of a formal terminal nitride complex of palladium. Photocrystallographic, magnetic, and computational characterization support the assignment as an authentic metallonitrene (Pd−N) with a diradical nitrogen ligand that is singly bonded to Pd II . Despite the subvalent nitrene character, selective C−H insertion with aldehydes follows nucleophilic selectivity. Transamidation of the benzamide product is enabled by reaction with N 3 SiMe 3 . Based on these results, a photocatalytic protocol for aldehyde C−H trimethylsilylamidation was developed that exhibits inverted, nucleophilic selectivity as compared to typical nitrene transfer catalysis. This first example of catalytic C−H nitrogen atom transfer offers facile access to primary amides after deprotection.

Schmidt‐Räntsch, Till↗

DOE OSTI2022

Nitrogen Atom Transfer Catalysis by Metallonitrene C−H Insertion: Photocatalytic Amidation of Aldehydes

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Materials Data on CsPd2Cl5 by Materials Project

CsPd2Cl5 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Cs1+ is bonded in a 9-coordinate geometry to nine Cl1- atoms. There are a spread of Cs–Cl bond distances ranging from 3.62–4.17 Å. Pd2+ is bonded in a rectangular see-saw-like geometry to four Cl1- atoms. There are a spread of Pd–Cl bond distances ranging from 2.30–2.36 Å. There are three inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a distorted L-shaped geometry to one Cs1+ and two equivalent Pd2+ atoms. In the second Cl1- site, Cl1- is bonded in a distorted single-bond geometry to three equivalent Cs1+ and one Pd2+ atom. In the third Cl1- site, Cl1- is bonded in a water-like geometry to one Cs1+ and two equivalent Pd2+ atoms.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Materials Data on K2Pd(NO2)4 by Materials Project

(K(NO2)2)2Pd crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional and consists of four palladium molecules and one K(NO2)2 framework. In the K(NO2)2 framework, there are two inequivalent K1+ sites. In the first K1+ site, K1+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of K–O bond distances ranging from 2.82–3.12 Å. In the second K1+ site, K1+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of K–O bond distances ranging from 2.73–3.34 Å. There are four inequivalent N3+ sites. In the first N3+ site, N3+ is bonded in a bent 120 degrees geometry to two O2- atoms. Both N–O bond lengths are 1.25 Å. In the second N3+ site, N3+ is bonded in a distorted bent 120 degrees geometry to two O2- atoms. There is one shorter (1.25 Å) and one longer (1.26 Å) N–O bond length. In the third N3+ site, N3+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.25 Å) and one longer (1.26 Å) N–O bond length. In the fourth N3+ site, N3+ is bonded in a distorted bent 120 degrees geometry to two O2- atoms. There is one shorter (1.25 Å) and one longer (1.26 Å) N–O bond length. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a 1-coordinate geometry to three K1+ and one N3+ atom. In the second O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent K1+ and one N3+ atom. In the third O2- site, O2- is bonded in a 1-coordinate geometry to two K1+ and one N3+ atom. In the fourth O2- site, O2- is bonded in a 1-coordinate geometry to two equivalent K1+ and one N3+ atom. In the fifth O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent K1+ and one N3+ atom. In the sixth O2- site, O2- is bonded in a distorted single-bond geometry to one K1+ and one N3+ atom. In the seventh O2- site, O2- is bonded in a distorted single-bond geometry to two K1+ and one N3+ atom. In the eighth O2- site, O2- is bonded in a distorted single-bond geometry to two K1+ and one N3+ atom.

36 MATERIALS SCIENCE↗