Modular Molecules: Site‐Selective Metal Substitution,Photoreduction, and Chirality in Polyoxometalate Hybrids |
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| Authors: | Michele Vonci Fateme Akhlaghi?Bagherjeri Peter D Hall Dr Robert W Gable Athanasios Zavras Prof Richard A J O'Hair Yuping Liu Dr Jie Zhang Dr Matthew R Field Dr Matthew B Taylor Prof Johan Du?Plessis Prof Gary Bryant Prof Mark Riley Dr Lorenzo Sorace Pablo A Aparicio Dr Xavier López Prof Josep M Poblet Dr Chris Ritchie Dr Colette Boskovic |
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| Institution: | 1. School of Chemistry, University of Melbourne, Parkville, 3010 (Australia);2. School of Chemistry, Monash University, Clayton, 3800 (Australia);3. School of Applied Sciences, RMIT University, Melbourne, 3001 (Australia);4. School of Chemistry and Molecular BioScience, University of Queensland, St. Lucia, 4072 (Australia);5. UdR INSTM & Department of Chemistry “U. Schiff”, University of Florence, 50019 Sesto Fiorentino (Italy);6. Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel?lí Domingo s/n, 43007 Tarragona (Spain) |
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| 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 : 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. |
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| Keywords: | amino acids chirality electronic structure photoreduction polyoxometalates |
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