Importance of solution equilibria in the directed assembly of metal chalcogenide mesostructures

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Abstract

We describe the new nanostructured Pt/Ge/Se materials prepared from the molecular units [Ge2Se6]4- and [GeSe 4]4- and linking Pt2+ ions in the presence of surfactant micelles. X-ray diffraction coupled with transmission electron microscopy images reveals hexagonal pore symmetry. The solvent dependence and solution speciation of these building blocks were investigated by means of multinuclear NMR spectroscopy and by fast atom bombardment (FAB) mass spectroscopy and it is shown that rapid exchange equilibrium is reached between species like [Ge4Se10]4-, [Ge 2Se6]4-, and [GeSe4]4- in both water and formamide. This results in multiple Ge/Se anions being incorporated in the mesostructured materials which is supported by Raman and IR spectroscopic data. It is likely that the presence of multiple building units both in water and formamide solutions favors the assembly of mesostructured metal chalcogenides with good pore order. Systematic variation of both surfactant headgroup and chain length modulates the optoelectronic properties of the mesostructures. The Pt/Ge/Se materials show sharp band gap transitions in the range of 1.24-1.97 eV. Finally, the materials exhibit reversible ion-exchange properties and a marked inorganic framework flexibility that enables a contraction-expansion process in response to the exchange. The Pt/Ge/Se framework possesses a very high surface area as estimated by small-angle X-ray scattering techniques.

Original languageEnglish
Pages (from-to)8366-8376
Number of pages11
JournalJournal of the American Chemical Society
Volume130
Issue number26
DOIs
Publication statusPublished - Jul 2 2008

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Surface-Active Agents
Metals
Fast Atom Bombardment Mass Spectrometry
Biomolecular Nuclear Magnetic Resonance
Water
Ion Exchange
Micelles
Transmission Electron Microscopy
X-Ray Diffraction
Anions
Surface active agents
Magnetic Resonance Spectroscopy
X-Rays
Ions
Chalcogenides
Electron transitions
X ray scattering
Chain length
Optoelectronic devices
Nuclear magnetic resonance spectroscopy

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Importance of solution equilibria in the directed assembly of metal chalcogenide mesostructures. / Bag, Santanu; Kanatzidis, Mercouri G.

In: Journal of the American Chemical Society, Vol. 130, No. 26, 02.07.2008, p. 8366-8376.

Research output: Contribution to journalArticle

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