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Directed Self‐Assembly, Symmetry Breaking, and Electronic Modulation of Metal Oxide Clusters by Pyramidal Heteroanions
Author(s) -
Sartzi Harikleia,
Long DeLiang,
Sproules Stephen,
Cronin Leroy,
Miras Haralampos N.
Publication year - 2018
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.201705711
Subject(s) - polyoxometalate , heteroatom , electron paramagnetic resonance , density functional theory , chemistry , thermogravimetric analysis , spectroscopy , crystallography , cluster (spacecraft) , analytical chemistry (journal) , computational chemistry , nuclear magnetic resonance , organic chemistry , quantum mechanics , computer science , programming language , catalysis , ring (chemistry) , physics
Abstract Mixed valence/metal polyoxometalate (POM) clusters are one of the most interesting host species because they show the ability to incorporate a wide range of heteroatoms of various charges and geometries. We report herein the incorporation of pyramidal EO 3 2− heteroanions (E=PH, S, Se, Te) that are responsible not only for directing the templated assembly of a family of mixed‐metal POMs but also for the symmetry‐breaking of the traditional Dawson architecture and modulation of the electronic characteristics of the cluster's shell. The isolated family of POMs consists of four members: (Me 2 NH 2 ) 5 Na 2 [Mo 11 V 7 O 52 (HPO 3 )] ⋅ MeOH ⋅ 5 H 2 O ( 1 ), (NH 4 ) 7 [Mo 11 V 7 O 52 (SO 3 )] ⋅ 12 H 2 O ( 2 ), K 7 [Mo 11 V 7 O 52 (SeO 3 )] ⋅ 31 H 2 O ( 3 ), and (Me 2 NH 2 ) 6 Na[Mo 11 V 7 O 52 (TeO 3 )] ⋅ 15 H 2 O ( 4 ), and were characterized by X‐ray structural analysis, electrospray ionization mass spectrometry (ESI‐MS), thermogravimetric analysis (TGA), UV/Vis, FTIR, elemental analysis, flame atomic absorption spectroscopy (FAAS), and inductively coupled plasma optical emission spectroscopy (ICP‐OES). Cyclic voltammetry (CV) and electron paramagnetic resonance (EPR) spectroscopic studies in concert with density functional theoretical (DFT) calculations have been used to elucidate the effect of the heteroatom on the electronic properties of the cluster.