Dimensional reductions from 2-D Nb{sub 4}P{sub 2}S{sub 21} to 1-D ANb{sub 2}PS{sub 10} (A=Na, K, Rb, Cs, Tl) and to 0-D Tl{sub 5}[Nb{sub 2}S{sub 4}C{sub l8}]Cl using halide molten salts

Journal Article · Fri Aug 15 04:00:00 EDT 2008 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2008.03.040· OSTI ID:21128376

Bang, Hyunjin; Kim, Youngmee; Kim, Seri ^[1]; Kim, Sung-Jin ^[1]

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1. Division of Nanosciences, Ewha Womans University, Seoul 120-750 (Korea, Republic of)

We found new synthetic routes to obtain 1-D quaternary thiophosphate compounds and a 0-D molecular complex containing a Nb{sub 2}S{sub 4} core from a 2-D ternary thiophosphate, Nb{sub 4}P{sub 2}S{sub 21}. When Nb{sub 4}P{sub 2}S{sub 21} was reacted with alkali metal halides (ACl; A=Na, K, Rb, Cs) or TlCl at 500-700 deg. C, the -S-S-S- bridges in 2-D Nb{sub 2}PS{sub 10}-S-S{sub 10}PNb{sub 2} were excised to form a 1-D chain, and cations were inserted between the chains to form ANb{sub 2}PS{sub 10} (A=Na, K, Rb, Cs, Tl). We also found that thallium chloride (TlCl) is an excellent reagent for further excision, and it substitutes chloride ligands for the sulfur ligands of 2-D Nb{sub 4}P{sub 2}S{sub 21} to form the molecular complex Tl{sub 5}[Nb{sub 2}S{sub 4}Cl{sub 8}]Cl. Crystal data for TlNb{sub 2}PS{sub 10}: monoclinic, Pn, a=6.9452(11) A, b=7.3761(12) A, 12.873(2) A, {beta}=104.472(3){sup o}, and Z=2. Crystal data for Tl{sub 5}[Nb{sub 2}S{sub 4}Cl{sub 8}]Cl: orthorhombic, Immm, a=7.001(5) A, b=9.509(7) A, c=15.546(11) A, and Z=2. - Graphical abstract: We developed new synthetic routes to obtain 1-D quaternary thiophosphate compounds and a molecular complex containing a Nb{sub 2}S{sub 4} core from a 2-D ternary thiophosphate, Nb{sub 4}P{sub 2}S{sub 21}. When Nb{sub 4}P{sub 2}S{sub 21} was reacted with alkali metal halides or TlCl, the -S-S-S- bridges in 2-D Nb{sub 2}PS{sub 10}-S-S{sub 10}PNb{sub 2} were excised to form a 1-D chain, and cations were inserted between the chains.

• OSTI ID: 21128376
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 8 Vol. 181; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CESIUM COMPOUNDS
CHLORIDES
CRYSTALS
LIGANDS
MOLTEN SALTS
MONOCLINIC LATTICES
NIOBIUM SULFIDES
ORTHORHOMBIC LATTICES
POTASSIUM COMPOUNDS
RUBIDIUM COMPOUNDS
SODIUM COMPOUNDS
TETRAGONAL LATTICES
THALLIUM CHLORIDES