[Ag2M(Te2O5)2]SO4 (M = CeIV or ThIV): A New Purely Inorganic d/f-Heterometallic Cationic Material

Poe, Todd N.; White, Frankie D.; Proust, Vanessa; Villa, Eric M.; Polinski, Matthew J.

doi:10.1021/acs.inorgchem.8b00504

Cited by 12 publications

(16 citation statements)

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“…Cationic materials are rare not only for f-block materials but also for materials in general, with the most well-known cationic materials being the layered double-hydroxides . The synthesis of cationic materials has been a goal of our research laboratories, and we are pleased to add several more into the expanding list of f-element-containing cationic materials. − The anion-exchange capability of [M 4 (C 4 O 4 ) 5 (H 2 O) 12 ]Cl 2 ·5H 2 O (M = Eu, Dy, Ho Er) is currently being investigated and will be reported elsewhere.…”

Section: Resultsmentioning

confidence: 99%

Trivalent f-Element Squarates, Squarate-Oxalates, and Cationic Materials, and the Determination of the Nine-Coordinate Ionic Radius of Cf(III)

et al. 2020

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The synthesis, structure, and solid-state UV–vis–NIR spectroscopy of four new f-element squarates, M2(C4O4)3(H2O)4 (M = Eu, Am, Cf) and Sm(C4O4)(C4O3OH)(H2O)2·0.5H2O, four new cationic lanthanide squarate chlorides, [M4(C4O4)5(H2O)12]Cl2·5H2O (M = Eu, Dy, Ho Er), and two new actinide squarate oxalates, M2(C4O4)2(C2O4)(H2O)4 (M = Am, Cf), are presented. All of the metal centers are trivalent. Single-crystal X-ray diffraction analysis reveals that M2(C4O4)3(H2O)4 and Sm(C4O4)(C4O3OH)(H2O)2·0.5H2O have a two-dimensional sheet structure constructed from MO7(H2O)2 monocapped square-antiprismatic (coordination number (CN) = 9) metal centers and SmO6(H2O)2 square-antiprismatic (CN = 8) metal centers, respectively, whereas M2(C4O4)2(C2O4)(H2O)4 have a three-dimensional (3D) structure constructed from MO7(H2O)2 monocapped square-antiprismatic (CN = 9) metal centers. Additionally, the cationic framework materials [M4(C4O4)5(H2O)12]Cl2·5H2O have a 3D structure constructed from two crystallographically unique MO5(H2O)3 square-antiprismatic (CN = 8) metal centers. In these structures, the squarate ligands bind to the metal centers with varying coordination modes and denticities. The results of this study provide another example of the nonparallel chemistry between the lanthanides and transplutonium elements. From the crystallographic data for the isotypic series M2(C4O4)3(H2O)4 (M = La–Nd, Sm, Eu) and the linear regression fit to a plot of the unit cell volume as a function of the cube of the ionic radius, the nine-coordinate ionic radius of Cf 3+ was determined to be 1.127 ± 0.003 Å. Finally, computational analysis of the americium and californium complexes M2(C4O4)3(H2O)4 and M2(C4O4)2(C2O4)(H2O)4 reveals three important attributes: (i) the 5f orbitals are nonbonding in all cases, with the bonding differences occurring with the empty 6d orbitals; (ii) the Cf complexes exhibit more covalent character than their Am counterparts; and (iii) there is more covalent character in the squarate-oxalate complexes than in the squarate complexes.

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Section: Resultsmentioning

confidence: 99%

Trivalent f-Element Squarates, Squarate-Oxalates, and Cationic Materials, and the Determination of the Nine-Coordinate Ionic Radius of Cf(III)

et al. 2020

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“…The Bond-valence-sum (BVS) calculation results of Ag/Hg(1), Ag(2), Ag (3), Se(1), Se (2) and Se(3) cations are 1.28, 0.96, 0.63, 4.0, 4.37, 6.09 (Table S2), respectively, proving that the oxidation states of Hg(1), Ag(1)-Ag(3), Se(1)-Se(2) and Se(3) are +2, +1, +4 and +6, respectively [43,44]. The deviation of Ag/Hg(1) from the ideal oxidation is mainly due to the low BVS of Ag atom, which is common in silver oxides [45][46][47][48][49]. The slightly higher valence for Se (2) can be attributed to the two short Se-O bonds (1.645 Å).…”

Section: Crystal Structure Of Ag 4 Hg(seo 3 ) 2 (Seo 4 ) (1)mentioning

confidence: 87%

“…The deviations of Ag(1) from the ideal oxidation can be attributed to their weak coordination bonds. If the Ag···O distances in the range of 2.7-3.0 Å are considered, the BVSs of the Ag(1) atoms are 0.74 [45][46][47][48][49]. The structure of compound 2 features a novel 3D bismuth selenite framework with 12-and 6-MPR tunnels along b axis (Fig.…”

Section: Crystal Structure Of Ag 4 Hg(seo 3 ) 2 (Seo 4 ) (1)mentioning

confidence: 99%

Ag4Hg(SeO3)2(SeO4): a novel SHG material created in mixed valent selenium oxides by in situ synthesis

Wang

et al. 2019

Sci. China Mater.

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Explorations of new second harmonic generation materials in Ag + -Hg 2+ /Bi 3+ -selenites systems afforded three new silver selenium oxides, namely, Ag 4 Hg(SeO 3 ) 2 (SeO 4 ) (1), Ag 2 Bi 2 (SeO 3 ) 3 (SeO 4 ) (2) and Ag 5 Bi(SeO 3 ) 4 (3). They exhibit flexible crystal chemistry. Compounds 1 and 2 are mixed valence selenium oxides containing Se(IV) and Se(VI) cations simultaneously. Compounds 1 and 3 exhibit a 3D open framework with 4-, 6-and 8-member polyhedral ring tunnels along a, b and c axes. Compound 1 crystallized in a polar space group and could display a subtle frequency doubling efficiency about 35% of the commercial KH 2 PO 4 (KDP). UV-vis-NIR spectra reveal that compounds 1-3 are wide-band semiconductors with the optical bandgaps of 3.11, 3.65, 3.58 eV respectively. Theoretical calculations disclose that compounds 2 and 3 are indirect band gap structures and their bandgaps are determined by Ag, Bi, Se and O atoms together.

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“…Recently, we have been working on a metal–SO 4 –TeO 3 system to expand the tetrahedral groups to sulfates, which were reported as the promising near-ultraviolet (UV) even deep-UV SHG materials. − The known sulfate tellurites were mainly converged on lanthanide compounds, which often crystallized in the CS space group because of their large coordination number. − Only one structure of Al 2 (OH) 2 TeO 3 SO 4 with group 13 elements was reported . Our efforts in the In(III)–SO 4 –TeO 3 system afford two new indium sulfate tellurites, namely, centrosymmetric In 2 (SO 4 )(TeO 3 )(OH) 2 (H 2 O) and non-centrosymmetric In 3 (SO 4 )(TeO 3 ) 2 F 3 (H 2 O).…”

Section: Introductionmentioning

confidence: 99%

Two Indium Sulfate Tellurites: Centrosymmetric In₂(SO₄)(TeO₃)(OH)₂(H₂O) and Non-centrosymmetric In₃(SO₄)(TeO₃)₂F₃(H₂O)

Gong

Ying

et al. 2019

Inorg. Chem.

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Two new indium sulfate tellurites, namely, In 2 (SO 4 )(TeO 3 )-(OH) 2 (H 2 O) and In 3 (SO 4 )(TeO 3 ) 2 F 3 (H 2 O), were synthesized by hydrothermal method in a one-pot reaction. Their pure phase yields have been successfully optimized to 76% and 21%, respectively. In 2 (SO 4 )(TeO 3 )-(OH) 2 (H 2 O) crystallized in centrosymmetric (CS) space group P2 1 /n, while In 3 (SO 4 )(TeO 3 ) 2 F 3 (H 2 O) formed a non-centrosymmetric (NCS) and chiral space group P2 1 2 1 2 1 . The CS compound features a 2D layered structure composed of 2D indium oxide layers decorated by sulfate tetrahedra and tellurite groups. The NCS compound displays a 3D network consisting of indium tellurite layers bridged by sulfate tetrahedra. Powder second harmonic generation measurements disclosed that In 3 (SO 4 )(TeO 3 ) 2 F 3 (H 2 O) exhibits a weak frequency-doubling efficiency about 11% of the commercial KDP. Its powder laser damage threshold quantity was estimated to be 79.6 MW/cm 2 , which is about 36 times that of AGS. The two samples present wide optical band gaps of 4.86 and 4.10 eV, respectively, which were determined by Te, In, and O atoms based on density functional theory calculations.

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[Ag₂M(Te₂O₅)₂]SO₄ (M = Ce^IV or Th^IV): A New Purely Inorganic d/f-Heterometallic Cationic Material

Cited by 12 publications

References 35 publications

Trivalent f-Element Squarates, Squarate-Oxalates, and Cationic Materials, and the Determination of the Nine-Coordinate Ionic Radius of Cf(III)

Trivalent f-Element Squarates, Squarate-Oxalates, and Cationic Materials, and the Determination of the Nine-Coordinate Ionic Radius of Cf(III)

Ag4Hg(SeO3)2(SeO4): a novel SHG material created in mixed valent selenium oxides by in situ synthesis

Two Indium Sulfate Tellurites: Centrosymmetric In₂(SO₄)(TeO₃)(OH)₂(H₂O) and Non-centrosymmetric In₃(SO₄)(TeO₃)₂F₃(H₂O)

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[Ag2M(Te2O5)2]SO4 (M = CeIV or ThIV): A New Purely Inorganic d/f-Heterometallic Cationic Material

Cited by 12 publications

References 35 publications

Trivalent f-Element Squarates, Squarate-Oxalates, and Cationic Materials, and the Determination of the Nine-Coordinate Ionic Radius of Cf(III)

Trivalent f-Element Squarates, Squarate-Oxalates, and Cationic Materials, and the Determination of the Nine-Coordinate Ionic Radius of Cf(III)

Ag4Hg(SeO3)2(SeO4): a novel SHG material created in mixed valent selenium oxides by in situ synthesis

Two Indium Sulfate Tellurites: Centrosymmetric In2(SO4)(TeO3)(OH)2(H2O) and Non-centrosymmetric In3(SO4)(TeO3)2F3(H2O)

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[Ag₂M(Te₂O₅)₂]SO₄ (M = Ce^IV or Th^IV): A New Purely Inorganic d/f-Heterometallic Cationic Material

Two Indium Sulfate Tellurites: Centrosymmetric In₂(SO₄)(TeO₃)(OH)₂(H₂O) and Non-centrosymmetric In₃(SO₄)(TeO₃)₂F₃(H₂O)