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DOE OSTI2020

Materials Data on KPr(ClO)4 by Materials Project

KPr(OCl)4 crystallizes in the orthorhombic P2_12_12 space group. The structure is three-dimensional. K is bonded in a 8-coordinate geometry to four O and four equivalent Cl atoms. There are two shorter (3.13 Å) and two longer (3.19 Å) K–O bond lengths. There are two shorter (3.10 Å) and two longer (3.59 Å) K–Cl bond lengths. Pr is bonded in a 6-coordinate geometry to two equivalent O and four Cl atoms. Both Pr–O bond lengths are 2.42 Å. There are two shorter (2.72 Å) and two longer (2.98 Å) Pr–Cl bond lengths. There are two inequivalent O sites. In the first O site, O is bonded in a 2-coordinate geometry to one K and one O atom. The O–O bond length is 1.24 Å. In the second O site, O is bonded in a distorted trigonal non-coplanar geometry to one K, one Pr, and one Cl atom. The O–Cl bond length is 1.68 Å. There are two inequivalent Cl sites. In the first Cl site, Cl is bonded in a distorted water-like geometry to one Pr and one O atom. In the second Cl site, Cl is bonded in a distorted trigonal planar geometry to two equivalent K and one Pr atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on RbNd(ClO)4 by Materials Project

RbNd(OCl)4 crystallizes in the orthorhombic P2_12_12 space group. The structure is three-dimensional. Rb is bonded in a 8-coordinate geometry to four O and four equivalent Cl atoms. There are two shorter (3.26 Å) and two longer (3.48 Å) Rb–O bond lengths. There are two shorter (3.18 Å) and two longer (3.69 Å) Rb–Cl bond lengths. Nd is bonded in a 6-coordinate geometry to two equivalent O and four Cl atoms. Both Nd–O bond lengths are 2.38 Å. There are two shorter (2.70 Å) and two longer (2.97 Å) Nd–Cl bond lengths. There are two inequivalent O sites. In the first O site, O is bonded in a bent 120 degrees geometry to one Rb and one O atom. The O–O bond length is 1.23 Å. In the second O site, O is bonded in a distorted water-like geometry to one Rb, one Nd, and one Cl atom. The O–Cl bond length is 1.68 Å. There are two inequivalent Cl sites. In the first Cl site, Cl is bonded in a distorted water-like geometry to one Nd and one O atom. In the second Cl site, Cl is bonded in a distorted trigonal planar geometry to two equivalent Rb and one Nd atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on RbCe(ClO)4 by Materials Project

RbCe(OCl)4 crystallizes in the orthorhombic P2_12_12 space group. The structure is three-dimensional. Rb is bonded in a 8-coordinate geometry to four O and four equivalent Cl atoms. There are two shorter (3.39 Å) and two longer (3.47 Å) Rb–O bond lengths. There are two shorter (3.26 Å) and two longer (3.66 Å) Rb–Cl bond lengths. Ce is bonded in a 8-coordinate geometry to four O and four Cl atoms. There are two shorter (2.35 Å) and two longer (2.41 Å) Ce–O bond lengths. There are two shorter (2.72 Å) and two longer (2.96 Å) Ce–Cl bond lengths. There are two inequivalent O sites. In the first O site, O is bonded in a 3-coordinate geometry to one Rb, one Ce, and one O atom. The O–O bond length is 1.31 Å. In the second O site, O is bonded in a distorted water-like geometry to one Rb, one Ce, and one Cl atom. The O–Cl bond length is 1.66 Å. There are two inequivalent Cl sites. In the first Cl site, Cl is bonded in a distorted water-like geometry to one Ce and one O atom. In the second Cl site, Cl is bonded in a trigonal planar geometry to two equivalent Rb and one Ce atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Hg5(ClO)4 by Materials Project

Hg5(OCl)4 crystallizes in the triclinic P-1 space group. The structure is two-dimensional and consists of one Hg5(OCl)4 sheet oriented in the (1, 0, 1) direction. there are three inequivalent Hg sites. In the first Hg site, Hg is bonded in a 2-coordinate geometry to two O and three Cl atoms. There are one shorter (2.12 Å) and one longer (2.17 Å) Hg–O bond lengths. There are a spread of Hg–Cl bond distances ranging from 2.80–3.02 Å. In the second Hg site, Hg is bonded in a linear geometry to two O and one Cl atom. There are one shorter (2.04 Å) and one longer (2.08 Å) Hg–O bond lengths. The Hg–Cl bond length is 3.07 Å. In the third Hg site, Hg is bonded in a linear geometry to two equivalent O atoms. Both Hg–O bond lengths are 2.07 Å. There are two inequivalent O sites. In the first O site, O is bonded in a trigonal non-coplanar geometry to three Hg atoms. In the second O site, O is bonded in a bent 120 degrees geometry to two Hg atoms. There are two inequivalent Cl sites. In the first Cl site, Cl is bonded in a 2-coordinate geometry to three Hg atoms. In the second Cl site, Cl is bonded in a distorted water-like geometry to one Hg and one Cl atom. The Cl–Cl bond length is 2.63 Å.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on CdCuH8(ClO)4 by Materials Project

CuCdH4(OCl2)2(H2O)2 crystallizes in the triclinic P-1 space group. The structure is two-dimensional and consists of two water molecules and one CuCdH4(OCl2)2 sheet oriented in the (0, 1, 0) direction. In the CuCdH4(OCl2)2 sheet, Cu2+ is bonded to two equivalent O2- and four equivalent Cl1- atoms to form distorted CuCl4O2 octahedra that share corners with four equivalent CdCl6 octahedra and edges with two equivalent CuCl4O2 octahedra. The corner-sharing octahedra tilt angles range from 49–52°. Both Cu–O bond lengths are 1.97 Å. There are two shorter (2.32 Å) and two longer (2.90 Å) Cu–Cl bond lengths. Cd2+ is bonded to six Cl1- atoms to form CdCl6 octahedra that share corners with four equivalent CuCl4O2 octahedra and edges with two equivalent CdCl6 octahedra. The corner-sharing octahedra tilt angles range from 49–52°. There are a spread of Cd–Cl bond distances ranging from 2.64–2.70 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. O2- is bonded in a distorted trigonal non-coplanar geometry to one Cu2+ and two H1+ atoms. There are two inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a 3-coordinate geometry to two equivalent Cu2+ and one Cd2+ atom. In the second Cl1- site, Cl1- is bonded in an L-shaped geometry to two equivalent Cd2+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Mo3H9Br3(ClO)4 by Materials Project

Mo3Br3Cl4H9O4 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of four hydrogen tetrahydrate molecules and two Mo3Br3Cl4 clusters. In each Mo3Br3Cl4 cluster, there are three inequivalent Mo2+ sites. In the first Mo2+ site, Mo2+ is bonded to one Br1- and four Cl1- atoms to form edge-sharing MoBrCl4 square pyramids. The Mo–Br bond length is 2.65 Å. There are a spread of Mo–Cl bond distances ranging from 2.57–2.62 Å. In the second Mo2+ site, Mo2+ is bonded to one Br1- and four Cl1- atoms to form edge-sharing MoBrCl4 square pyramids. The Mo–Br bond length is 2.63 Å. There are a spread of Mo–Cl bond distances ranging from 2.57–2.63 Å. In the third Mo2+ site, Mo2+ is bonded to one Br1- and four Cl1- atoms to form distorted edge-sharing MoBrCl4 trigonal bipyramids. The Mo–Br bond length is 2.58 Å. There are a spread of Mo–Cl bond distances ranging from 2.69–2.81 Å. There are three inequivalent Br1- sites. In the first Br1- site, Br1- is bonded in a single-bond geometry to one Mo2+ atom. In the second Br1- site, Br1- is bonded in a distorted single-bond geometry to one Mo2+ atom. In the third Br1- site, Br1- is bonded in a single-bond geometry to one Mo2+ atom. There are four inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a 3-coordinate geometry to three Mo2+ atoms. In the second Cl1- site, Cl1- is bonded in a 3-coordinate geometry to three Mo2+ atoms. In the third Cl1- site, Cl1- is bonded in a 3-coordinate geometry to three Mo2+ atoms. In the fourth Cl1- site, Cl1- is bonded in a 3-coordinate geometry to three Mo2+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LaGd3(ClO)4 by Materials Project

Gd3La(OCl)4 is Matlockite-derived structured and crystallizes in the orthorhombic Amm2 space group. The structure is three-dimensional. there are two inequivalent Gd3+ sites. In the first Gd3+ site, Gd3+ is bonded in a 9-coordinate geometry to four O2- and five Cl1- atoms. There are two shorter (2.28 Å) and two longer (2.30 Å) Gd–O bond lengths. There are four shorter (3.12 Å) and one longer (3.25 Å) Gd–Cl bond lengths. In the second Gd3+ site, Gd3+ is bonded in a 4-coordinate geometry to four O2- and five Cl1- atoms. There are one shorter (2.29 Å) and three longer (2.30 Å) Gd–O bond lengths. There are a spread of Gd–Cl bond distances ranging from 3.13–3.20 Å. La3+ is bonded in a 9-coordinate geometry to four O2- and five Cl1- atoms. There are two shorter (2.37 Å) and two longer (2.39 Å) La–O bond lengths. There are one shorter (3.12 Å) and four longer (3.15 Å) La–Cl bond lengths. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded to two equivalent Gd3+ and two equivalent La3+ atoms to form OLa2Gd2 tetrahedra that share corners with four OGd4 tetrahedra and edges with four equivalent OLaGd3 tetrahedra. In the second O2- site, O2- is bonded to four Gd3+ atoms to form OGd4 tetrahedra that share corners with four OLa2Gd2 tetrahedra and edges with four equivalent OLaGd3 tetrahedra. In the third O2- site, O2- is bonded to three Gd3+ and one La3+ atom to form OLaGd3 tetrahedra that share corners with four equivalent OLaGd3 tetrahedra and edges with four OLa2Gd2 tetrahedra. There are three inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a 5-coordinate geometry to four equivalent Gd3+ and one La3+ atom. In the second Cl1- site, Cl1- is bonded in a 5-coordinate geometry to five Gd3+ atoms. In the third Cl1- site, Cl1- is bonded in a 5-coordinate geometry to three Gd3+ and two equivalent La3+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on BaCd(ClO)4 by Materials Project

BaCd(OCl)4 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. Ba is bonded in a 8-coordinate geometry to two O and six Cl atoms. There are one shorter (3.36 Å) and one longer (3.40 Å) Ba–O bond lengths. There are a spread of Ba–Cl bond distances ranging from 3.05–3.78 Å. Cd is bonded to six Cl atoms to form edge-sharing CdCl6 octahedra. There are a spread of Cd–Cl bond distances ranging from 2.65–2.73 Å. There are four inequivalent O sites. In the first O site, O is bonded in a bent 150 degrees geometry to one Ba and one O atom. The O–O bond length is 1.23 Å. In the second O site, O is bonded in a single-bond geometry to one O atom. In the third O site, O is bonded in a bent 150 degrees geometry to one Ba and one O atom. The O–O bond length is 1.23 Å. In the fourth O site, O is bonded in a single-bond geometry to one O atom. There are four inequivalent Cl sites. In the first Cl site, Cl is bonded in a distorted trigonal non-coplanar geometry to one Ba and two equivalent Cd atoms. In the second Cl site, Cl is bonded in a distorted trigonal non-coplanar geometry to one Ba and two equivalent Cd atoms. In the third Cl site, Cl is bonded in a distorted water-like geometry to two equivalent Ba and one Cd atom. In the fourth Cl site, Cl is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ba and one Cd atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on NaH6RuN(ClO)4 by Materials Project

(NaRuNH2O4Cl3)2(H2)3(HCl)2 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of four hydrochloric acid molecules, six hydrogen molecules, and four NaRuNH2O4Cl3 clusters. In each NaRuNH2O4Cl3 cluster, Na1+ is bonded in a 4-coordinate geometry to two O2- and two Cl1- atoms. There are one shorter (2.26 Å) and one longer (3.07 Å) Na–O bond lengths. There are one shorter (2.68 Å) and one longer (2.82 Å) Na–Cl bond lengths. Ru2+ is bonded in a distorted T-shaped geometry to one H1+ and two Cl1- atoms. The Ru–H bond length is 1.56 Å. There are one shorter (2.26 Å) and one longer (2.37 Å) Ru–Cl bond lengths. 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. There are two inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one Ru2+ atom. In the second H1+ site, H1+ is bonded in a single-bond geometry to one Cl1- atom. The H–Cl bond length is 1.29 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 120 degrees geometry to one Na1+ and one N3+ atom. In the second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Na1+ and one O2- atom. The O–O bond length is 1.24 Å. In the third O2- site, O2- is bonded in a single-bond geometry to one N3+ atom. In the fourth O2- site, O2- is bonded in a single-bond geometry to one O2- atom. There are three inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a distorted bent 150 degrees geometry to one Na1+ and one Ru2+ atom. In the second Cl1- site, Cl1- is bonded in a distorted water-like geometry to one Na1+ and one H1+ atom. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one Ru2+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Na3W2(ClO)4 by Materials Project

Na3W2(OCl)4 crystallizes in the orthorhombic Amm2 space group. The structure is three-dimensional. there are three inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded in a 9-coordinate geometry to four equivalent O2- and five Cl1- atoms. All Na–O bond lengths are 2.84 Å. There are a spread of Na–Cl bond distances ranging from 2.85–3.04 Å. In the second Na1+ site, Na1+ is bonded in a 9-coordinate geometry to four equivalent O2- and five Cl1- atoms. All Na–O bond lengths are 2.76 Å. There are a spread of Na–Cl bond distances ranging from 2.85–3.05 Å. In the third Na1+ site, Na1+ is bonded in a 9-coordinate geometry to four equivalent O2- and five Cl1- atoms. All Na–O bond lengths are 2.75 Å. There are a spread of Na–Cl bond distances ranging from 2.87–3.12 Å. There are two inequivalent W+4.50+ sites. In the first W+4.50+ site, W+4.50+ is bonded to four equivalent O2- and two Cl1- atoms to form distorted corner-sharing WCl2O4 octahedra. The corner-sharing octahedral tilt angles are 5°. All W–O bond lengths are 2.04 Å. There are one shorter (2.45 Å) and one longer (2.56 Å) W–Cl bond lengths. In the second W+4.50+ site, W+4.50+ is bonded to four equivalent O2- and two Cl1- atoms to form distorted corner-sharing WCl2O4 octahedra. The corner-sharing octahedral tilt angles are 5°. All W–O bond lengths are 1.97 Å. There are one shorter (2.43 Å) and one longer (2.51 Å) W–Cl bond lengths. O2- is bonded to three Na1+ and two W+4.50+ atoms to form distorted ONa3W2 square pyramids that share corners with three equivalent ClNa5W octahedra, corners with two equivalent ClNa4W square pyramids, corners with three equivalent ONa3W2 square pyramids, edges with three equivalent ONa3W2 square pyramids, a faceface with one ClNa5W octahedra, a faceface with one ClNa4W square pyramid, and faces with two equivalent ONa3W2 square pyramids. The corner-sharing octahedra tilt angles range from 45–51°. There are four inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded to five Na1+ and one W+4.50+ atom to form distorted ClNa5W octahedra that share corners with four equivalent ClNa5W octahedra, corners with twelve equivalent ONa3W2 square pyramids, edges with four equivalent ClNa4W square pyramids, and faces with four equivalent ONa3W2 square pyramids. The corner-sharing octahedra tilt angles range from 22–23°. In the second Cl1- site, Cl1- is bonded to four Na1+ and one W+4.50+ atom to form distorted ClNa4W square pyramids that share corners with four equivalent ClNa4W square pyramids, corners with eight equivalent ONa3W2 square pyramids, edges with four equivalent ClNa5W octahedra, and faces with four equivalent ONa3W2 square pyramids. In the third Cl1- site, Cl1- is bonded in a distorted square co-planar geometry to three Na1+ and one W+4.50+ atom. In the fourth Cl1- site, Cl1- is bonded in a distorted square co-planar geometry to three Na1+ and one W+4.50+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on CoH18C4N8(ClO)4 by Materials Project

CoC4N8H18(OCl)4 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of two CoC4N8H18(OCl)4 clusters. Co2+ is bonded in an octahedral geometry to two equivalent O2- and four Cl1- atoms. Both Co–O bond lengths are 2.15 Å. There are two shorter (2.38 Å) and two longer (2.54 Å) Co–Cl bond lengths. There are two inequivalent C4+ sites. In the first C4+ site, C4+ is bonded in a trigonal planar geometry to two N3- and one O2- atom. There is one shorter (1.33 Å) and one longer (1.40 Å) C–N bond length. The C–O bond length is 1.26 Å. In the second C4+ site, C4+ is bonded in a trigonal planar geometry to three N3- atoms. There is two shorter (1.33 Å) and one longer (1.36 Å) C–N bond length. There are four inequivalent N3- sites. In the first N3- site, N3- is bonded in a trigonal planar geometry to one C4+ and two H1+ atoms. Both N–H bond lengths are 1.02 Å. In the second N3- site, N3- is bonded in a trigonal planar geometry to one C4+ and two H1+ atoms. There is one shorter (1.02 Å) and one longer (1.03 Å) N–H bond length. In the third N3- site, N3- is bonded in a trigonal planar geometry to two C4+ and one H1+ atom. The N–H bond length is 1.03 Å. In the fourth N3- site, N3- is bonded in a trigonal planar geometry to one C4+ and two H1+ atoms. Both N–H bond lengths are 1.02 Å. There are nine inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to two O2- atoms. There is one shorter (1.01 Å) and one longer (1.68 Å) H–O bond length. In the second H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the third 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 fourth H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the fifth H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the sixth H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the seventh H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the eighth H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the ninth H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted water-like geometry to one Co2+ and two H1+ atoms. In the second O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one C4+ and one H1+ atom. There are two inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one Co2+ atom. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one Co2+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on MnH18C4N8(ClO)4 by Materials Project

MnC4N8H18(OCl)4 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of two MnC4N8H18(OCl)4 clusters. Mn2+ is bonded in an octahedral geometry to two equivalent O2- and four Cl1- atoms. Both Mn–O bond lengths are 2.16 Å. There are two shorter (2.45 Å) and two longer (2.54 Å) Mn–Cl bond lengths. There are two inequivalent C4+ sites. In the first C4+ site, C4+ is bonded in a trigonal planar geometry to two N3- and one O2- atom. There is one shorter (1.33 Å) and one longer (1.40 Å) C–N bond length. The C–O bond length is 1.26 Å. In the second C4+ site, C4+ is bonded in a trigonal planar geometry to three N3- atoms. There is two shorter (1.33 Å) and one longer (1.36 Å) C–N bond length. There are four inequivalent N3- sites. In the first N3- site, N3- is bonded in a trigonal planar geometry to one C4+ and two H1+ atoms. Both N–H bond lengths are 1.02 Å. In the second N3- site, N3- is bonded in a trigonal planar geometry to one C4+ and two H1+ atoms. There is one shorter (1.02 Å) and one longer (1.03 Å) N–H bond length. In the third N3- site, N3- is bonded in a trigonal planar geometry to two C4+ and one H1+ atom. The N–H bond length is 1.03 Å. In the fourth N3- site, N3- is bonded in a trigonal planar geometry to one C4+ and two H1+ atoms. Both N–H bond lengths are 1.02 Å. There are nine inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to two O2- atoms. There is one shorter (1.00 Å) and one longer (1.70 Å) H–O bond length. In the second H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the third 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 fourth H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the fifth H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the sixth H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the seventh H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the eighth H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the ninth H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted water-like geometry to one Mn2+ and two H1+ atoms. In the second O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one C4+ and one H1+ atom. There are two inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one Mn2+ atom. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one Mn2+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Anion Binding by Macrocyclic Receptors: Computational Landscape of 1:1 and 2:1 Stoichiometries

Macrocyclic receptors play a crucial role in supramolecular chemistry, enabling the selective binding of guest molecules through non-covalent interactions. This study investigates the anion binding properties of three shape-persistent macrocycles, triazolophane, cyanostar, and tricarb, each featuring preorganized cavities with polarized CH hydrogen bond donors. In the 1:1 binding stoichiometries, the macrocycles preferentially bind anions that fit inside their two-dimensional cavities, with this preference being more pronounced in solution. Specifically, the triazolophane favors smaller anions like chloride and bromide, while the larger cavities offered by cyanostar and tricarb macrocycles preferentially bind the larger iodide. For large, polyatomic anions (SCN − , BF$^{−}_{4}$, ClO$^{−}_{4}$, and PF$^{−}_{6}$), the macrocycles self-assemble to form stable 2:1 sandwich complexes, exhibiting stronger binding. This shift in selectivity highlights the versatility of the macrocycles, making them promising candidates for anion sensing and regulation with various complexation stoichiometries.

Che, Minwei [Indiana University, Bloomington, IN (↗
DOE OSTI2021

Use of a Lewis acid, a Brønsted acid, and their binary mixtures for the hydrothermal liquefaction of lignocellulose

The main objective of the present study is to investigate the effect of a Lewis acid, Brønsted acid, and their combined use on the hydrothermal liquefaction of lignocellulosic biomass. Hydrothermal liquefaction of teak wood was conducted at 250, 300 and 350 °C for 15, 30 and 60 min. Hydrothermal liquefaction of teak wood was carried out at 300 °C for 30 min (the best optimum conditions) without and with the use of Mg(ClO 4 ) 2 , HClO 4 , and HClO 4 /Mg(ClO 4 ) 2 at various loadings (2–10 mmol/15 g wood). The highest bio-oil yield was obtained with the non-catalytic run. All tested catalysts have negative effect on bio-oil yields. The bio-oil yields generally decreased with increasing the catalyst loadings. The deoxygenation degree in bio-oils changed depending on the type of catalyst and loading. A high degree of de-oxygenation took place with Mg(ClO 4 ) 2 catalysts. An increased catalyst loading led to decreased aromatic contents of bio-oils catalyzed by either Mg(ClO 4 ) 2 or HClO 4 . The use of a catalyst increased total naphtha fractions in bio-oils. The highest heating value of the bio-oil was estimated to be approximately 30 MJ/kg. Gas chromatography–mass spectrometry analysis revealed that the bio-oils from the non-catalytic and catalytic runs contained aldehydes, ketones, phenols, acids, esters and alcohols. Furthermore, the relative yields of the oxygenated compounds were affected by catalyst type.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Isotopic discrimination of natural and anthropogenic perchlorate sources in groundwater in a semi-arid region of northeastern Oregon (USA)

Perchlorate (ClO 4 - ) has synthetic and natural sources. Synthetic ClO 4 - is released to the environment from its use as an oxidant in military and aerospace applications, and from its presence in a variety of common commercial products, such as safety flares, chlorate herbicides, and fireworks. Natural sources of ClO 4 - in the environment include imported nitrate fertilizers derived from salt deposits in the Atacama Desert of Chile and indigenous natural ClO 4 - that accumulates in unsaturated soils and groundwaters in other arid and semi-arid environments, largely from atmospheric deposition. The stable isotope ratios of chlorine ( 37 Cl/ 35 Cl) and oxygen ( 18 O/ 16 O, 17 O/ 16 O) and the isotopic abundance of radioactive 36 Cl in ClO 4 - can be used to discriminate these different sources. Perchlorate was previously detected at relatively high concentrations (3.8–34.7 μg/L) in groundwater from many wells in the Boardman-Umatilla area near the Columbia River in northeastern Oregon, which is a semi-arid, highly agricultural, heavily irrigated area that includes several past and current military installations. Eight representative groundwater wells were sampled throughout this region and isotopic characteristics of ClO 4 - collected from each well were measured along with other chemical and isotopic parameters including tritium and other groundwater age indicators. We report isotopic data indicate that indigenous natural ClO 4 - was present in groundwater from all sampled wells and was the predominant source in five of the wells. Synthetic ClO 4 - was present in the three remaining wells with natural ClO 4 - , and a minor fraction of Atacama-fertilizer-derived ClO4- was indicated in one of the wells. Data from this study expand the geographic area of the USA in which indigenous natural ClO 4 - has been detected to include the semi-arid northwest. This study also illustrates the role of irrigation recharge as a mechanism for producing relatively high concentrations of indigenous natural ClO 4 - in groundwater by flushing accumulated salts from the unsaturated zone.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Origin of the isotopic composition of natural perchlorate: Experimental results for the impact of reaction pathway and initial ClO x reactant

Natural perchlorate (ClO 4 - ) exists in many places on Earth, in lunar regolith, meteorites, and on the surface of Mars. Terrestrial natural ClO 4 - has widely variable Cl and O stable isotopic compositions (δ 37 Cl, δ 18 O, Δ 17 O). The δ 18 O and Δ 17 O values of ClO 4 - from the most hyper-arid locations co-vary. ClO 4 - from less arid areas has relatively little 17 O excess and poor Δ 17 O-δ 18 O correlation. ClO 4 - from the Atacama Desert has unusually low δ 37 Cl (<-10‰) and exhibits a positive correlation between δ 37 Cl and δ 18 O, while the δ 37 Cl of ClO 4 - from all other locations varies between -5 and +7‰ with no δ 37 Cl-δ 18 O covariation. To evaluate the impact of different precursors (ClO x ) and reaction pathways on the isotopic composition of ClO 4 - , we measured the isotopic composition of ClO 4 - produced in the laboratory by UV or O 3 mediated aqueous oxidation of Cl-, OCl-, ClO2-, and ClO2° as well as O 3 mediated oxidation of dry NaCl. ClO x oxidation in aqueous or dry systems enriched in O 3 produced ClO 4 - with Δ 17 O values that generally increased with the number of O atoms required and included evidence that the site-specific 17 O anomaly in O 3 was preferentially transferred to ClO 4 - . Based on the inferred number of O atoms sourced from O 3 , and known Cl and O reaction pathways, it appears that ClO 2 ° and ClO 3 * were required intermediates in the production of ClO 4 - in the O 3 experiments. ClO x aqueous oxidation by UV irradiation produced ClO 4 - with a large range of δ 18 O values and little or no 17 O anomaly. ClO 3 - was produced to a much greater extent than ClO 4 - in all experiments except dry oxidation of NaCl by O 3 . The isotopic composition of ClO 3 - was distinct from that of ClO 4 - produced from the same initial reactants. Combined results of O 3 and UV mediated reactions largely bracketed the range of natural ClO 4 - δ 18 O and Δ 17 O values as well as δ 37 Cl values of non-Atacama natural samples, but no conditions produced the low δ 37 Cl values of Atacama ClO 4 - . Finally, our results indicate that variation in production mechanisms, possibly combined with isotopically variable precursors, could be responsible for much of the observed isotopic variation in natural ClO 4 - and ClO 3 - .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗