Modular molecules: site-selective metal substitution, photoreduction, and chirality in polyoxometalate hybrids

Vonci, Michele, Bagherjeri, Fateme Akhlaghi, 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 L, Poblet, Josep M., Ritchie, Chris and Boskovic, Colette (2014) Modular molecules: site-selective metal substitution, photoreduction, and chirality in polyoxometalate hybrids. Chemistry: A European Journal, 20 43: 14102-14111. doi:10.1002/chem.201403222

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Author Vonci, Michele
Bagherjeri, Fateme Akhlaghi
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 L
Poblet, Josep M.
Ritchie, Chris
Boskovic, Colette
Title Modular molecules: site-selective metal substitution, photoreduction, and chirality in polyoxometalate hybrids
Journal name Chemistry: A European Journal   Check publisher's open access policy
ISSN 0947-6539
1521-3765
Publication date 2014-09-09
Sub-type Article (original research)
DOI 10.1002/chem.201403222
Open Access Status
Volume 20
Issue 43
Start page 14102
End page 14111
Total pages 11
Place of publication Weinheim, Germany
Publisher Wiley - V C H Verlag
Collection year 2015
Language eng
Formatted abstract
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: ʟ-Nle, 2 a; ᴅ-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.
Keyword Amino acids
Chirality
Electronic structure
Photoreduction
Polyoxometalates
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ
Additional Notes Article first published online: 9 SEP 2014

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2015 Collection
School of Chemistry and Molecular Biosciences
 
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Created: Fri, 19 Sep 2014, 12:45:58 EST by Mrs Louise Nimwegen on behalf of School of Chemistry & Molecular Biosciences