Modular Molecules: Site-Selective Metal Substitution, Photoreduction, and Chirality in Polyoxometalate Hybrids

The first members of a promising new family of hybrid amino acid–polyoxometalates have emerged from a search for modular functional molecules. Incorporation of glycine (Gly) or norleucine (Nle) ligands into an yttrium‐tungstoarsenate structural backbone, followed by crystallization with p‐methylbenz...

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Published in:Chemistry : a European journal Vol. 20; no. 43; pp. 14102 - 14111
Main Authors: Vonci, Michele, Akhlaghi Bagherjeri, Fateme, Hall, Peter D., Gable, Robert W., Zavras, Athanasios, O'Hair, Richard A. J., Liu, Yuping, Zhang, Jie, Field, Matthew R., Taylor, Matthew B., Du Plessis, Johan, Bryant, Gary, Riley, Mark, Sorace, Lorenzo, Aparicio, Pablo A., López, Xavier, Poblet, Josep M., Ritchie, Chris, Boskovic, Colette
Format: Journal Article
Language:English
Published: Weinheim WILEY-VCH Verlag 20.10.2014
WILEY‐VCH Verlag
Wiley Subscription Services, Inc
Subjects:
Amino acids
Cations
Chemistry
Chirality
Circular dichroism
Crystallization
Dichroism
Electrochemistry
electronic structure
Glycine
Hybrids
Ligands
Materials substitution
Modular
Nanostructure
Norleucine
Photochemistry
Photoreduction
Polyanions
Polyelectrolytes
polyoxometalates
Polyoxometallates
Searching
Spectrometry
Spectroscopy
Yttrium
photoreduction
chirality
polyoxometalates
amino acids
electronic structure
ISSN:0947-6539, 1521-3765, 1521-3765
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Summary:The first members of a promising new family of hybrid amino acid–polyoxometalates have emerged from a search for modular functional molecules. Incorporation of glycine (Gly) or norleucine (Nle) ligands into an yttrium‐tungstoarsenate structural backbone, followed by crystallization with p‐methylbenzylammonium (p‐MeBzNH3+) cations, affords (p‐MeBzNH3)6K2(GlyH)[AsIII4(YIIIWVI3)WVI44YIII4O159(Gly)8‐ (H2O)14]⋅47 H2O (1) and enantiomorphs (p‐MeBzNH3)15(NleH)3 [AsIII4(MoV2MoVI2)WVI44YIII4O160(Nle)9(H2O)11][AsIII4(MoVI2WVI2)‐ WVI44YIII4O160(Nle)9(H2O)11] (generically designated 2: L‐Nle, 2 a; D‐Nle, 2 b). An intensive structural, spectroscopic, electrochemical, magnetochemical and theoretical investigation has allowed the elucidation of site‐selective metal substitution and photoreduction of the tetranuclear core of the hybrid polyanions. In the solid state, markedly different crystal packing is evident for the compounds, which indicates the role of noncovalent interactions involving the amino acid ligands. In solution, mass spectrometric and small‐angle X‐ray scattering studies confirm maintenance of the structure of the polyanions of 2, while circular dichroism demonstrates that the chirality is also maintained. The combination of all of these features in a single modular family emphasizes the potential of such hybrid polyoxometalates to provide nanoscale molecular materials with tunable properties. Modular molecules: The first members of a modular family of hybrid amino acid–polyoxometalates have been investigated by a variety of physical techniques. The apparent site‐selective metal substitution, photoreduction, chirality, and directable solid‐state packing highlight the remarkable tunability of the structural features and ensuing physical properties of this new family of molecules and thus their potential for the development of functional molecular materials (see figure).
Bibliography:Australian Research Council - No. DP0877704; No. DP110100155; No. LE120100186
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ArticleID:CHEM201403222
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
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ISSN:0947-6539
1521-3765
1521-3765
DOI:10.1002/chem.201403222