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Title: LiSi 3 As 6 and Li 2 SiAs 2 with flexible SiAs 2 polyanions: synthesis, structure, bonding, and ionic conductivity

Abstract

Two novel ternary phases, LiSi 3 As 6 and Li 2 SiAs 2 , have been synthesized and characterized.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [1];  [3]; ORCiD logo [1]
  1. Department of Chemistry, Iowa State University, Ames, USA, Ames Laboratory
  2. Department of Chemistry, University of California, Davis, Davis, USA
  3. Department of Materials Science and Engineering, University of California, Davis, Davis, USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1594197
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Published Article
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Name: Journal of Materials Chemistry. A Journal Volume: 8 Journal Issue: 6; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English

Citation Formats

Mark, Justin, Lee, Kathleen, Marple, Maxwell A. T., Lee, Shannon, Sen, Sabyasachi, and Kovnir, Kirill. LiSi 3 As 6 and Li 2 SiAs 2 with flexible SiAs 2 polyanions: synthesis, structure, bonding, and ionic conductivity. United Kingdom: N. p., 2020. Web. doi:10.1039/C9TA11150F.
Mark, Justin, Lee, Kathleen, Marple, Maxwell A. T., Lee, Shannon, Sen, Sabyasachi, & Kovnir, Kirill. LiSi 3 As 6 and Li 2 SiAs 2 with flexible SiAs 2 polyanions: synthesis, structure, bonding, and ionic conductivity. United Kingdom. doi:10.1039/C9TA11150F.
Mark, Justin, Lee, Kathleen, Marple, Maxwell A. T., Lee, Shannon, Sen, Sabyasachi, and Kovnir, Kirill. Tue . "LiSi 3 As 6 and Li 2 SiAs 2 with flexible SiAs 2 polyanions: synthesis, structure, bonding, and ionic conductivity". United Kingdom. doi:10.1039/C9TA11150F.
@article{osti_1594197,
title = {LiSi 3 As 6 and Li 2 SiAs 2 with flexible SiAs 2 polyanions: synthesis, structure, bonding, and ionic conductivity},
author = {Mark, Justin and Lee, Kathleen and Marple, Maxwell A. T. and Lee, Shannon and Sen, Sabyasachi and Kovnir, Kirill},
abstractNote = {Two novel ternary phases, LiSi 3 As 6 and Li 2 SiAs 2 , have been synthesized and characterized.},
doi = {10.1039/C9TA11150F},
journal = {Journal of Materials Chemistry. A},
number = 6,
volume = 8,
place = {United Kingdom},
year = {2020},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C9TA11150F

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Works referenced in this record:

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margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Mark, Justin; Wang, Jian; Wu, Kui</span> </li> <li> Journal of the American Chemical Society, Vol. 141, Issue 30</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1021/jacs.9b04653" class="text-muted" target="_blank" rel="noopener noreferrer">10.1021/jacs.9b04653<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div><div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1039/C2EE23355J" target="_blank" rel="noopener noreferrer" class="name">Phase stability, electrochemical stability and ionic conductivity of the Li <sub>10±1</sub> MP <sub>2</sub> X <sub>12</sub> (M = Ge, Si, Sn, Al or P, and X = O, S or Se) family of superionic conductors<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="2013-01-01">January 2013</span></small> </h2> <ul class="small references-list" style="list-style-type:none; 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Sci., Vol. 6, Issue 1</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1039/C2EE23355J" class="text-muted" target="_blank" rel="noopener noreferrer">10.1039/C2EE23355J<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div><div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1016/j.jpowsour.2014.07.159" target="_blank" rel="noopener noreferrer" class="name">Synthesis, structure and lithium ionic conductivity of solid solutions of Li10(Ge1−M )P2S12 (M = Si, Sn)<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="2014-12-01">December 2014</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Kato, Yuki; Saito, Ryoko; Sakano, Mitsuru</span> </li> <li> Journal of Power Sources, Vol. 271</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1016/j.jpowsour.2014.07.159" class="text-muted" target="_blank" rel="noopener noreferrer">10.1016/j.jpowsour.2014.07.159<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div><div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.3891/acta.chem.scand.19-1232" target="_blank" rel="noopener noreferrer" class="name">The Crystal Structure of SiAs.<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="1965-01-01">January 1965</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Wadsten, Tommy; Burmester, S.; Cederberg, G.</span> </li> <li> Acta Chemica Scandinavica, Vol. 19</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.3891/acta.chem.scand.19-1232" class="text-muted" target="_blank" rel="noopener noreferrer">10.3891/acta.chem.scand.19-1232<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div><div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1002/anie.199718081" target="_blank" rel="noopener noreferrer" class="name">ELF: The Electron Localization Function<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="1997-09-17">September 1997</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Savin, Andreas; Nesper, Reinhard; Wengert, Steffen</span> </li> <li> Angewandte Chemie International Edition in English, Vol. 36, Issue 17</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1002/anie.199718081" class="text-muted" target="_blank" rel="noopener noreferrer">10.1002/anie.199718081<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div></div> <div class="pagination-container small"> <a class="pure-button prev page" href="#" rel="prev"><span class="fa fa-angle-left"></span></a><ul class="pagination d-inline-block" style="padding-left:.2em;"></ul><a class="pure-button next page" href="#" rel="next"><span class="fa fa-angle-right"></span></a> </div> </div> </div> <div class="col-sm-3 order-sm-3"> <ul class="nav nav-stacked"> <li class="active"><a href="" class="reference-type-filter tab-nav" data-tab="biblio-references" data-filter="type" data-pattern="*"><span class="fa fa-angle-right"></span> All References</a></li> <li class="small" style="margin-left:.75em; 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float:none;">[ × clear filter / sort ]</a> </div> </form> </div> </div> </div> </section> <section id="biblio-related" class="tab-content tab-content-sec " data-tab="biblio"> <div class="row"> <div class="col-sm-9 order-sm-9"> <section id="biblio-similar" class="tab-content tab-content-sec active" data-tab="related"> <div class="padding"> <p class="lead text-muted" style="font-size: 18px; margin-top:0px;">Similar records in OSTI.GOV collections:</p> <aside> <ul class="item-list" itemscope itemtype="http://schema.org/ItemList" style="padding-left:0; list-style-type: none;"> <li> <div class="article item document" itemprop="itemListElement" itemscope itemtype="http://schema.org/WebPage"><meta itemprop="position" content="0" /><div class="item-info"> <h2 class="title" itemprop="name headline"><a href="/pages/biblio/22012089-synthesis-structural-characterization-ternary-zintl-phases-ae-sub-al-sub-pn-sub-ae-sub-ga-sub-pn-sub-ae-ca-sr-ba-eu-pn" itemprop="url">Synthesis and structural characterization of the ternary Zintl phases AE{sub 3}Al{sub 2}Pn{sub 4} and AE{sub 3}Ga{sub 2}Pn{sub 4} (AE=Ca, Sr, Ba, Eu; Pn=P, As)</a></h2> <div class="metadata"> <small class="text-muted" style="text-transform:uppercase;display:block;line-height:2.5em;">Journal Article</small><span class="authors"> <span class="author">He, Hua</span> ; <span class="author">Tyson, Chauntae</span> ; <span class="author">Saito, Maia</span> ; <span class="author">...</span> <span class="text-muted pubdata"> - Journal of Solid State Chemistry</span> </span> </div> <div class="abstract">Ten new ternary phosphides and arsenides with empirical formulae AE{sub 3}Al{sub 2}Pn{sub 4} and AE{sub 3}Ga{sub 2}Pn{sub 4} (AE=Ca, Sr, Ba, Eu; Pn=P, As) have been synthesized using molten Ga, Al, and Pb fluxes. They have been structurally characterized by single-crystal and powder X-ray diffraction to form with two different structures-Ca{sub 3}Al{sub 2}P{sub 4}, Sr{sub 3}Al{sub 2}As{sub 4}, Eu{sub 3}Al{sub 2}P{sub 4}, Eu{sub 3}Al{sub 2}As{sub 4}, Ca{sub 3}Ga{sub 2}P{sub 4}, Sr{sub 3}Ga{sub 2}P{sub 4}, Sr{sub 3}Ga{sub 2}As{sub 4}, and Eu{sub 3}Ga{sub 2}As{sub 4} crystallize with the Ca{sub 3}Al{sub 2}As{sub 4} structure type (space group C2/c, Z=4); Ba{sub 3}Al{sub 2}P{sub 4}<a href='#' onclick='$(this).hide().next().show().next().show();return false;' style='margin-left:10px;'>more »</a><span style='display:none;'> and Ba{sub 3}Al{sub 2}As{sub 4} adopt the Na{sub 3}Fe{sub 2}S{sub 4} structure type (space group Pnma, Z=4). The polyanions in both structures are made up of TrPn{sub 4} tetrahedra, which share common corners and edges to form {sup 2}{sub {infinity}}[TrPn{sub 2}]{sub 3-} layers in the phases with the Ca{sub 3}Al{sub 2}As{sub 4} structure, and {sup 1}{sub {infinity}}[TrPn{sub 2}]{sub 3-} chains in Ba{sub 3}Al{sub 2}P{sub 4} and Ba{sub 3}Al{sub 2}As{sub 4} with the Na{sub 3}Fe{sub 2}S{sub 4} structure type. The valence electron count for all of these compounds follows the Zintl-Klemm rules. Electronic band structure calculations confirm them to be semiconductors. - Graphical abstract: AE{sub 3}Al{sub 2}Pn{sub 4} and AE{sub 3}Ga{sub 2}Pn{sub 4} (AE=Ca, Sr, Ba, Eu; Pn=P, As) crystallize in two different structures-Ca{sub 3}Al{sub 2}P{sub 4}, Sr{sub 3}Al{sub 2}As{sub 4}, Eu{sub 3}Al{sub 2}P{sub 4}, Eu{sub 3}Al{sub 2}As{sub 4}, Ca{sub 3}Ga{sub 2}P{sub 4}, Sr{sub 3}Ga{sub 2}P{sub 4}, Sr{sub 3}Ga{sub 2}As{sub 4}, and Eu{sub 3}Ga{sub 2}As{sub 4}, are isotypic with the previously reported Ca{sub 3}Al{sub 2}As{sub 4} (space group C2/c (No. 15)), while Ba{sub 3}Al{sub 2}P{sub 4} and Ba{sub 3}Al{sub 2}As{sub 4} adopt a different structure known for Na{sub 3}Fe{sub 2}S{sub 4} (space group Pnma (No. 62). The polyanions in both structures are made up of TrPn{sub 4} tetrahedra, which by sharing common corners and edges, form {sup 2}{sub {infinity}}[TrPn{sub 2}]{sub 3-}layers in the former and {sup 1}{sub {infinity}}[TrPn{sub 2}]{sub 3-} chains in Ba{sub 3}Al{sub 2}P{sub 4} and Ba{sub 3}Al{sub 2}As{sub 4}. Highlights: Black-Right-Pointing-Pointer AE{sub 3}Ga{sub 2}Pn{sub 4} (AE=Ca, Sr, Ba, Eu; Pn=P, As) are new ternary pnictides. Black-Right-Pointing-Pointer Ba{sub 3}Al{sub 2}P{sub 4} and Ba{sub 3}Al{sub 2}As{sub 4} adopt the Na{sub 3}Fe{sub 2}S{sub 4} structure type. Black-Right-Pointing-Pointer The Sr- and Ca-compounds crystallize with the Ca{sub 3}Al{sub 2}As{sub 4} structure type. Black-Right-Pointing-Pointer The valence electron count for all title compounds follows the Zintl-Klemm rules.</span><a href='#' onclick='$(this).hide().prev().hide().prev().show();return false;' style='margin-left:10px;display:none;'>« less</a></div><div class="metadata-links small clearfix text-muted" style="margin-top:15px;"> <div class="pure-menu pure-menu-horizontal pull-right" style="width:unset;"> <ul class="pure-menu-list"> <li class="pure-menu-item"><span class="item-info-ftlink">DOI: <a class="misc doi-link " href="https://doi.org/10.1016/J.JSSC.2012.01.042" target="_blank" rel="noopener" title="Link to document DOI" data-ostiid="22012089" data-product-type="Journal Article" data-product-subtype="AC" >10.1016/J.JSSC.2012.01.042</a></span></li> </ul> </div> </div> </div> <div class="clearfix"></div> </div> </li> <li> <div class="article item document" itemprop="itemListElement" itemscope itemtype="http://schema.org/WebPage"><meta itemprop="position" content="1" /><div class="item-info"> <h2 class="title" itemprop="name headline"><a href="/pages/biblio/22658154-ionic-asi-sub-sub-li-na-rb-stabilized-covalent-sin-bonding-first-principles-calculations" itemprop="url">Ionic ASi{sub 2}N{sub 3} (A=Li, Na, K and Rb) stabilized by the covalent Si–N bonding: First-principles calculations</a></h2> <div class="metadata"> <small class="text-muted" style="text-transform:uppercase;display:block;line-height:2.5em;">Journal Article</small><span class="authors"> <span class="author">Zhang, Huijun</span> ; <span class="author">Ren, Jiadong, E-mail: jdren@ysu.edu.cn</span> ; <span class="author">Wu, Lailei</span> ; <span class="author">...</span> <span class="text-muted pubdata"> - Journal of Solid State Chemistry</span> </span> </div> <div class="abstract">The structural, elastic and electronic properties of LiSi{sub 2}N{sub 3} and its substitutions by Na, K and Rb were investigated through first-principles computations. The expansion of lattice parameters of ASi{sub 2}N{sub 3} from Li, Na, K to Rb is found to be determined by the bond angle of Si–N1–Si, which suggests a possible way to improve the lithium ionic conductivity by substitutions. ASi{sub 2}N{sub 3} (A=Li, Na, K and Rb) shows the similar elastic behaviors, while the electronic band gap gradually decreases from 5.1 to 3.4 eV from LiSi{sub 2}N{sub 3} to RbSi{sub 2}N{sub 3}. Interestingly, the analysis of electronic<a href='#' onclick='$(this).hide().next().show().next().show();return false;' style='margin-left:10px;'>more »</a><span style='display:none;'> structure, crystal orbital Hamiltonian populations and Bader charges shows that the covalence of Si–N bonding is critical for the stability of ASi{sub 2}N{sub 3} phase. Among ASi{sub 2}N{sub 3} phases, there is a relatively high ionicity in NaSi{sub 2}N{sub 3}; the Si–N bond strength in [Si{sub 2}N{sub 3}]{sup −} net for KSi{sub 2}N{sub 3} and RbSi{sub 2}N{sub 3} is comparable to LiSi{sub 2}N{sub 3}, but stronger than NaSi{sub 2}N{sub 3}. - Graphic abstract: Universal trend of structural and electronic properties in alkaline metal silicon nitrides, ASi{sub 2}N{sub 3}, A=Li, Na, K and Rb. - Highlights: • Trend in structure, electronic and mechanical properties of ASi{sub 2}N{sub 3} (A=Li-Rb) were predicted. • Lattice expansion of ASi{sub 2}N{sub 3} induced by the bond angle of Si–N1–Si was found. • Calculated band gap decreases from 5.1 to 3.4 eV from LiSi{sub 2}N{sub 3} to RbSi{sub 2}N{sub 3}. • Covalent Si–N bonding is critical for the stability of ASi{sub 2}N{sub 3}.</span><a href='#' onclick='$(this).hide().prev().hide().prev().show();return false;' style='margin-left:10px;display:none;'>« less</a></div><div class="metadata-links small clearfix text-muted" style="margin-top:15px;"> <div class="pure-menu pure-menu-horizontal pull-right" style="width:unset;"> <ul class="pure-menu-list"> <li class="pure-menu-item"><span class="item-info-ftlink">DOI: <a class="misc doi-link " href="https://doi.org/10.1016/J.JSSC.2016.10.020" target="_blank" rel="noopener" title="Link to document DOI" data-ostiid="22658154" data-product-type="Journal Article" data-product-subtype="AC" >10.1016/J.JSSC.2016.10.020</a></span></li> </ul> </div> </div> </div> <div class="clearfix"></div> </div> </li> <li> <div class="article item document" itemprop="itemListElement" itemscope itemtype="http://schema.org/WebPage"><meta itemprop="position" content="2" /><div class="item-info"> <h2 class="title" itemprop="name headline"><a href="/pages/biblio/22658202-synthesis-structure-novel-lithium-ion-conductor-li-sub-ge-sub-ps-sub" itemprop="url">Synthesis and structure of novel lithium-ion conductor Li{sub 7}Ge{sub 3}PS{sub 12}</a></h2> <div class="metadata"> <small class="text-muted" style="text-transform:uppercase;display:block;line-height:2.5em;">Journal Article</small><span class="authors"> <span class="author">Inoue, Yuki</span> ; <span class="author">Suzuki, Kota</span> ; <span class="author">Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8502</span> ; <span class="author">...</span> <span class="text-muted pubdata"> - Journal of Solid State Chemistry</span> </span> </div> <div class="abstract">The novel lithium-ion conductor Li{sub 7}Ge{sub 3}PS{sub 12} was synthesized by slow cooling from the ternary Li{sub 2}S–GeS{sub 2}–P{sub 2}S{sub 5} system, and was shown to exhibit a cubic argyrodite-type structure. The phase composition was determined by varying the ratio of starting materials; the observed monophasic properties were close to those for the Li{sub 7}Ge{sub 3}PS{sub 12} composition. The lattice parameter (a =9.80192(3) Å) of Li{sub 7}Ge{sub 3}PS{sub 12} was slightly smaller than that of Li{sub 7}PS{sub 6} (a =9.993 Å), indicating that substitution of a Li cation by the smaller Ge cation contracted the cubic lattice. In addition, the<a href='#' onclick='$(this).hide().next().show().next().show();return false;' style='margin-left:10px;'>more »</a><span style='display:none;'> novel structure consisted of a framework composed of four isolated (Ge/P)S{sub 4} tetrahedra. Li{sup +} ions occupied tetrahedral sites within the framework, forming a three-dimensional conduction pathway. Finally, Li{sub 7}Ge{sub 3}PS{sub 12} exhibited a high ionic conductivity of 1.1×10{sup −4} S cm{sup −1} at 25 °C and an activation energy of 25 kJ mol{sup −1}. - Graphical abstract: A novel Li{sub 7}Ge{sub 3}PS{sub 12} solid lithium ion conductor, with cubic argyrodite strucuture, shows high ion conductivity of 1.1×10{sup –4} S cm{sup –1} with an activation energy of 25 kJ mol{sup –1}. The argyrodite structure consists of (Ge/P)S{sub 4} tetrahedra units along with partial occupation of lithium and germanium at 48 h site. - Highlights: • A novel lithium-ion conductor Li{sub 7}Ge{sub 3}PS{sub 12} was detected. • This was achieved through slow cooling of the ternary Li{sub 2}S–GeS{sub 2}–P{sub 2}S{sub 5} system. • This novel conductor revealed a cubic argyrodite-type structure. • Li{sub 7}Ge{sub 3}PS{sub 12} exhibited a high ionic conductivity of 1.1×10{sup −4} S cm{sup −1} at 25 °C. • These properties will aid in the design of superior lithium-ion conductors.</span><a href='#' onclick='$(this).hide().prev().hide().prev().show();return false;' style='margin-left:10px;display:none;'>« less</a></div><div class="metadata-links small clearfix text-muted" style="margin-top:15px;"> <div class="pure-menu pure-menu-horizontal pull-right" style="width:unset;"> <ul class="pure-menu-list"> <li class="pure-menu-item"><span class="item-info-ftlink">DOI: <a class="misc doi-link " href="https://doi.org/10.1016/J.JSSC.2016.12.001" target="_blank" rel="noopener" title="Link to document DOI" data-ostiid="22658202" data-product-type="Journal Article" data-product-subtype="AC" >10.1016/J.JSSC.2016.12.001</a></span></li> </ul> </div> </div> </div> <div class="clearfix"></div> </div> </li> <li> <div class="article item document" itemprop="itemListElement" itemscope itemtype="http://schema.org/WebPage"><meta itemprop="position" content="3" /><div class="item-info"> <h2 class="title" itemprop="name headline"><a href="/pages/biblio/1471222-from-nonexistent-polar-intermetallic-pt3pr4-via-pt2xpr3-pt-sn-pr-ternaries" itemprop="url">From the Nonexistent Polar Intermetallic Pt <sub>3</sub>Pr <sub>4</sub> via Pt <sub>2–<em>x</em></sub>Pr <sub>3</sub> to Pt/Sn/Pr Ternaries</a></h2> <div class="metadata"> <small class="text-muted" style="text-transform:uppercase;display:block;line-height:2.5em;">Journal Article</small><span class="authors"> <span class="author">Rhodehouse, Melissa L.</span> ; <span class="author">Bell, Thomas</span> ; <span class="author">Smetana, Volodymyr</span> ; <span class="author">...</span> <span class="text-muted pubdata"> - Inorganic Chemistry</span> </span> </div> <div class="abstract">Here the Pt–Pr phase diagram has been explored well, recent work on rare-earth metal cluster halides with endohedral transition metal atoms has provided a new binary intermetallic that is nonexistent in the known phase diagram: The binary Pt <sub>3</sub>Pr <sub>4</sub> ( <b>1</b>) crystallizes in a new structure type ( <em>mP</em>56, <em>P</em>2 <sub>1</sub>/c, a = 12.353(2) Å, <em>b</em> = 7.4837(9) Å, c = 17.279(2) Å, β = 118.003(7)°, Z = 8) with six crystallographically independent Pt as well as eight Pr positions. The subsequent detailed investigation has led to another previously unreported, binary phase with the Ga <sub>2</sub>Gd <sub>3</sub> structure type, Pt <sub>2–x</sub>Pr <sub>3</sub> ( <b>2</b>, <em>tI</em>80, <em>I</em>4/ <em>mcm</em>, a = 11.931(9) Å, c = 14.45(1) Å, Z = 16), that is practically overlapping with the rhombohedral Pt <sub>2</sub>Pr <sub>3</sub> existing in the phase diagram. Application of different tin containing fluxes to reproduce the newly detected phases brought about two almost iso-compositional ternary compounds with Sn, Pt <sub>4</sub>Sn <sub>6</sub>Pr <sub>2.91</sub> ( <b>3</b>), and Pt <sub>4</sub>Sn <sub>6</sub>Pr <sub>3</sub> ( <b>4</b>), as well as Pt <sub>12</sub>Sn <sub>24</sub>Pr <sub>4.84</sub> ( <b>5</b>). <b>3</b> is a representative of the Pt <sub>4</sub>Ge <sub>6</sub>Ce <sub>3</sub> type ( <em>oP</em>52, <em>Pnma</em>, <em>a</em> = 7.2863(3) Å, b = 4.4909(2) Å, c = 35.114(2) Å), while 4 represents a new variant of the prolific <em>T</em> <sub>4</sub> <em>E</em> <sub>6</sub> <em>R</em> <sub>3</sub> family (T = transition metal, E = main group (semi)metal, R = rare-earth metal; Pt <sub>4</sub>Sn <sub>6</sub>Pr <sub>3</sub>: <em>oP</em>52, <em>Pnma</em>, a = 27.623(1) Å, b = 4.5958(2) Å, c = 9.3499(5) Å). Pt <sub>12</sub>Sn <sub>24</sub>Pr <sub>5–x</sub> ( <b>5</b>) crystallizes as a variant of the Ni <sub>8</sub>Sn <sub>16</sub>Gd <sub>3</sub> type ( <em>cI</em>82, <em>Im</em><a href='#' onclick='$(this).hide().next().show().next().show();return false;' style='margin-left:10px;'>more »</a><span style='display:none;'> $$\bar{3}$$, a = 12.274(1) Å, Z = 2). Electronic structure calculations provide hints on the origin of the structural changes (pseudo-polymorphism) for Pt <sub>x</sub>Pr <sub>3</sub> with x = 1.97 and 2.00, respectively, and reveal that heteroatomic Pt–Pr bonding strongly dominates in both binaries while the addition of the reactive metal tin leads to dominating Pt–Sn bonding interactions in the ternaries; Pt–Pt bonding interactions are strong but represent a minority in the binaries and are not present at all in the ternaries.</span><a href='#' onclick='$(this).hide().prev().hide().prev().show();return false;' style='margin-left:10px;display:none;'>« less</a></div><div class="metadata-links small clearfix text-muted" style="margin-top:15px;"> <span class="fa fa-book text-muted" aria-hidden="true"></span> Cited by 2<div class="pure-menu pure-menu-horizontal pull-right" style="width:unset;"> <ul class="pure-menu-list"> <li class="pure-menu-item"><span class="item-info-ftlink">DOI: <a class="misc doi-link " href="https://doi.org/10.1021/acs.inorgchem.8b01121" target="_blank" rel="noopener" title="Link to document DOI" data-ostiid="1471222" data-product-type="Journal Article" data-product-subtype="AM" >10.1021/acs.inorgchem.8b01121</a></span></li> <li class="pure-menu-item"><span class="item-info-ftlink"><a class="misc fulltext-link " href="/pages/servlets/purl/1471222" title="Link to document media" target="_blank" rel="noopener" data-ostiid="1471222" data-product-type="Journal Article" data-product-subtype="AM" >Full Text Available</a></span></li> </ul> </div> </div> </div> <div class="clearfix"></div> </div> </li> <li> <div class="article item document" itemprop="itemListElement" itemscope itemtype="http://schema.org/WebPage"><meta itemprop="position" content="4" /><div class="item-info"> <h2 class="title" itemprop="name headline"><a href="/pages/biblio/1361562-r3au9pn-gdtm-pn-sb-bi-link-between-cu10sn3-gd14ag51" itemprop="url"><i>R</i> <sub>3</sub>Au <sub>9</sub> <i>Pn</i> ( <i>R</i> = Y, Gd–Tm; <i>Pn</i> = Sb, Bi): A Link between Cu <sub>10</sub>Sn <sub>3</sub> and Gd <sub>14</sub>Ag <sub>51</sub></a></h2> <div class="metadata"> <small class="text-muted" style="text-transform:uppercase;display:block;line-height:2.5em;">Journal Article</small><span class="authors"> <span class="author">Celania, Chris</span> ; <span class="author">Smetana, Volodymyr</span> ; <span class="author">Provino, Alessia</span> ; <span class="author">...</span> <span class="text-muted pubdata"> - Inorganic Chemistry</span> </span> </div> <div class="abstract">A new series of intermetallic compounds <i>R</i> <sub>3</sub>Au <sub>9</sub> <i>Pn</i> ( <i>R</i> = Y, Gd–Tm; <i>Pn</i> = Sb, Bi) has been discovered during the explorations of the Au-rich parts of rare-earth-containing ternary systems with p-block elements. The existence of the series is strongly restricted by both geometric and electronic factors. <i>R</i> <sub>3</sub>Au <sub>9</sub> <i>Pn</i> compounds crystallize in the hexagonal crystal system with space group <i>P</i>6 <sub>3</sub>/m (a = 8.08–8.24 Å, c = 8.98–9.08 Å). All compounds feature Au- <i>Pn</i>, formally anionic, networks built up by layers of alternating edge-sharing Au@Au <sub>6</sub> and Sb@Au <sub>6</sub> trigonal antiprisms of overall composition Au<a href='#' onclick='$(this).hide().next().show().next().show();return false;' style='margin-left:10px;'>more »</a><span style='display:none;'> <sub>6/2</sub> <i>Pn</i> connected through additional Au atoms and separated by a triangular cationic substructure formed by <i>R</i> atoms. From a first look, the series appears to be isostructural with recently reported <i>R</i> <sub>3</sub>Au <sub>7</sub>Sn <sub>3</sub> (a ternary ordered derivative of the Cu <sub>10</sub>Sn <sub>3-</sub>structure type), but no example of <i>R</i> <sub>3</sub>Au <sub>9</sub>M is known when M is a triel or tetrel element. <i>R</i> <sub>3</sub>Au <sub>9</sub> <i>Pn</i> also contains Au@Au <sub>6</sub>Au <sub>2</sub> <i>R</i> <sub>3</sub> fully capped trigonal prisms, which are found to be isostructural with those found in the well-researched <i>R</i> <sub>14</sub>Au <sub>51</sub> series. This structural motif, not present in <i>R</i> <sub>3</sub>Au <sub>7</sub>Sn <sub>3</sub>, represents a previously unrecognized link between Cu <sub>10</sub>Sn <sub>3</sub> and Gd <sub>14</sub>Ag <sub>51</sub> parent structure types. Magnetic property measurements carried out for Ho <sub>3</sub>Au <sub>9</sub>Sb reveal a complex magnetic structure characterized by antiferromagnetic interactions at low temperature ( <i>T</i> <sub>N</sub> = 10 K). Two metamagnetic transitions occur at high field with a change from antiferromagnetic toward ferromagnetic ordering. Density functional theory based computations were performed to understand the materials’ properties and to shed some light on the stability ranges. As a result, this allowed a better understanding of the bonding pattern, especially of the Au-containing substructure, and elucidation of the role of the third element in the stability of the structure type.</span><a href='#' onclick='$(this).hide().prev().hide().prev().show();return false;' style='margin-left:10px;display:none;'>« less</a></div><div class="metadata-links small clearfix text-muted" style="margin-top:15px;"> <span class="fa fa-book text-muted" aria-hidden="true"></span> Cited by 2<div class="pure-menu pure-menu-horizontal pull-right" style="width:unset;"> <ul class="pure-menu-list"> <li class="pure-menu-item"><span class="item-info-ftlink">DOI: <a class="misc doi-link " href="https://doi.org/10.1021/acs.inorgchem.7b00898" target="_blank" rel="noopener" title="Link to document DOI" data-ostiid="1361562" data-product-type="Journal Article" data-product-subtype="PA" >10.1021/acs.inorgchem.7b00898</a></span></li> </ul> </div> </div> </div> <div class="clearfix"></div> </div> </li> </ul> </aside> </div> </section> </div> <div class="col-sm-3 order-sm-3"> <ul class="nav nav-stacked"> <li class="active"><a class="tab-nav disabled" data-tab="related" style="color: #636c72 !important; opacity: 1;"><span class="fa fa-angle-right"></span> Similar Records</a></li> </ul> </div> </div> </section> </div></div> </div> </div> </section> <footer class="" style="background-color:#f9f9f9; /* padding-top: 0.5rem; */"> <div class="footer-minor"> <div class="container"> <hr class="footer-separator" /> <div class="text-center" style="margin-top:1.25rem;"> <div class="pure-menu pure-menu-horizontal"> <ul class="pure-menu-list" id="footer-org-menu"> <li class="pure-menu-item"> <a href="https://energy.gov" target="_blank" rel="noopener noreferrer"> <img src="data:image/gif;base64,R0lGODlhAQABAIAAAP///wAAACH5BAEAAAAALAAAAAABAAEAAAICRAEAOw==" class="sprite sprite-footer-us-doe-min" alt="U.S. Department of Energy" /> </a> </li> <li class="pure-menu-item"> <a href="https://www.energy.gov/science/office-science" target="_blank" rel="noopener noreferrer"> <img src="data:image/gif;base64,R0lGODlhAQABAIAAAP///wAAACH5BAEAAAAALAAAAAABAAEAAAICRAEAOw==" class="sprite sprite-footer-office-of-science-min" alt="Office of Science" /> </a> </li> <li class="pure-menu-item"> <a href="/"> <img src="data:image/gif;base64,R0lGODlhAQABAIAAAP///wAAACH5BAEAAAAALAAAAAABAAEAAAICRAEAOw==" class="sprite sprite-footer-osti-min" alt="Office of Scientific and Technical Information" /> </a> </li> </ul> </div> </div> <div class="text-center small" style="margin-top:0.5em;margin-bottom:2.0rem;"> <div class="pure-menu pure-menu-horizontal"> <ul class="pure-menu-list"> <li class="pure-menu-item"><a href="/disclaim" class="pure-menu-link"><span class="fa fa-institution"></span> Website Policies <span class="hidden-xs">/ Important Links</span></a></li> <li class="pure-menu-item"><a href="/pages/contact" class="pure-menu-link"><span class="fa fa-comments-o"></span> Contact Us</a></li> <li class="d-block d-md-none"></li> <li class="pure-menu-item"><a href="https://www.facebook.com/ostigov" target="_blank" rel="noopener noreferrer" class="pure-menu-link social"><span class="fa fa-facebook" style=""></span></a></li> <li class="pure-menu-item"><a href="https://twitter.com/OSTIgov" target="_blank" rel="noopener noreferrer" class="pure-menu-link social"><span class="fa fa-twitter" style=""></span></a></li> <li class="pure-menu-item"><a href="https://www.youtube.com/user/ostigov" target="_blank" rel="noopener noreferrer" class="pure-menu-link social"><span class="fa fa-youtube-play" style=""></span></a></li> </ul> </div> </div> </div> </div> </footer> <link href="/pages/css/pages.fonts.200113.2012.css" rel="stylesheet"> <script src="/pages/js/pages.200113.2012.js"></script><noscript></noscript> <script defer src="/pages/js/pages.biblio.200113.2012.js"></script><noscript></noscript> <script defer src="/pages/js/lity.js"></script><noscript></noscript><script async type="text/javascript" src="/pages/js/Universal-Federated-Analytics-Min.js?agency=DOE" id="_fed_an_ua_tag"></script><noscript></noscript></body> <!-- DOE PAGES v.200113.2012 --> </html>