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Modular Molecules: Site‐Selective Metal Substitution, Photoreduction, and Chirality in Polyoxometalate Hybrids
Author(s) -
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
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201403222
Subject(s) - polyoxometalate , chirality (physics) , crystallography , chemistry , stereochemistry , molecule , crystal structure , enantiomer , metal , circular dichroism , catalysis , organic chemistry , chiral symmetry breaking , physics , quantum mechanics , nambu–jona lasinio model , quark
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 ‐MeBzNH 3 + ) cations, affords ( p ‐MeBzNH 3 ) 6 K 2 (GlyH)[As III 4 (Y III W VI 3 )W VI 44 Y III 4 O 159 (Gly) 8 ‐ (H 2 O) 14 ] ⋅ 47 H 2 O ( 1 ) and enantiomorphs ( p ‐MeBzNH 3 ) 15 (NleH) 3 [As III 4 (Mo V 2 Mo VI 2 )W VI 44 Y III 4 O 160 (Nle) 9 (H 2 O) 11 ][As III 4 (Mo VI 2 W VI 2 )‐ W VI 44 Y III 4 O 160 (Nle) 9 (H 2 O) 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.