Periodic hexagonal mesostructured chalcogenides based on platinum and [SnSe4]4- and [SnTe4]4- precursors. Solvent dependence of nanopore and wall organization

Pantelis N. Trikalitis, Thomas Bakas, Mercouri G Kanatzidis

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Abstract

Mesostructured chalcogenide-based materials with long-range order and semiconducting properties can be prepared using suitable molecular building blocks, linkage metal ions and surfactant molecules. In this paper we present surfactant templated, open framework platinum tin selenide and telluride materials assembled using K4SnQ4 (Q = Se, Te) salts and K2PtCl4 as precursors and a study of pore and wall organization. We find that materials prepared in water exhibit disordered pore organization, whereas those prepared in formamide are long-range ordered with hexagonal symmetry. In formamide the [SnQ4]4- anions undergo condensation-oligomerization reactions that produce different chalcogenido molecular species, whereas in water the anions remain intact. In addition to solvent, the pore organization and overall quality of the mesostructured materials strongly depend on the surfactant molecules, i.e., chain length and headgroup size. For example, highly ordered mesostructured platinum tin selenides with hexagonal symmetry were obtained using the hydroxyl-functionalized surfactants CnH2n+1N(CH 3)(CH2CH2OH)2Br (n = 16, 18, and 20), but when the headgroup was triethylammonium, hexagonal pore order was achieved only for n = 20 and not for n = 16 and 18. The experimental results imply that in order to achieve highly ordered chalcogenide frameworks a single building anionic block might be insufficient. Finally, we also report the first examples of hexagonal mesostructured Pt/Sn/Te materials based on K4SnTe4 as the precursor. The tellurides behave differently for their selenium analogues and have very low energy band gaps, in the range 0.5-0.7 eV.

Original languageEnglish
Pages (from-to)3910-3920
Number of pages11
JournalJournal of the American Chemical Society
Volume127
Issue number11
DOIs
Publication statusPublished - Mar 23 2005

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Nanopores
Chalcogenides
Platinum
Surface-Active Agents
Surface active agents
Tin
Anions
Negative ions
Water
Selenium
Oligomerization
Molecules
Hydroxyl Radical
Chain length
Salts
Metals
Band structure
Metal ions
Ions
Condensation

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Periodic hexagonal mesostructured chalcogenides based on platinum and [SnSe4]4- and [SnTe4]4- precursors. Solvent dependence of nanopore and wall organization",
abstract = "Mesostructured chalcogenide-based materials with long-range order and semiconducting properties can be prepared using suitable molecular building blocks, linkage metal ions and surfactant molecules. In this paper we present surfactant templated, open framework platinum tin selenide and telluride materials assembled using K4SnQ4 (Q = Se, Te) salts and K2PtCl4 as precursors and a study of pore and wall organization. We find that materials prepared in water exhibit disordered pore organization, whereas those prepared in formamide are long-range ordered with hexagonal symmetry. In formamide the [SnQ4]4- anions undergo condensation-oligomerization reactions that produce different chalcogenido molecular species, whereas in water the anions remain intact. In addition to solvent, the pore organization and overall quality of the mesostructured materials strongly depend on the surfactant molecules, i.e., chain length and headgroup size. For example, highly ordered mesostructured platinum tin selenides with hexagonal symmetry were obtained using the hydroxyl-functionalized surfactants CnH2n+1N(CH 3)(CH2CH2OH)2Br (n = 16, 18, and 20), but when the headgroup was triethylammonium, hexagonal pore order was achieved only for n = 20 and not for n = 16 and 18. The experimental results imply that in order to achieve highly ordered chalcogenide frameworks a single building anionic block might be insufficient. Finally, we also report the first examples of hexagonal mesostructured Pt/Sn/Te materials based on K4SnTe4 as the precursor. The tellurides behave differently for their selenium analogues and have very low energy band gaps, in the range 0.5-0.7 eV.",
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AU - Bakas, Thomas

AU - Kanatzidis, Mercouri G

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