Tuning the thermodynamic stability of oxothiomolybdenum wheels: Crystal structures, studies in solution and DFT calculations

被引：23
作者：
Institut Lavoisier de Versailles, UMR 8180, University of Versailles, 45 avenue des Etats-Unis, 78035 Versailles, France [1 ]
不详 [2 ]
机构：
[1] Institut Lavoisier de Versailles, UMR 8180, University of Versailles, 78035 Versailles
[2] Laboratoire de Chimie Quantique, Institut de Chimie, CNRS-ULP, 67000 Strasbourg
来源：
Dalton Trans. | 2008年 / 34卷 / 4565-4574期
关键词：
47;
D O I：
10.1039/b801716f
中图分类号：
学科分类号：
摘要：
The complexes [Mo12O12S12(OH) 12(Muco)]2- (Muco2- = muconate, C 6H4O42-) and [Mo12O 12S12(OH)12(TMT)]2- (TMT 2- = tetramethylterephthalate, C12H12O 42-) have been obtained from the condensation of the [Mo2O2S2]2+ building block in the presence of Muco2- and TMT2-, respectively. Both compounds were structurally characterized, revealing host-guest architectures with one or two encapsulated water molecules. 1H NMR spectra in DMSO and D 2O showed that both complexes had an average symmetry higher than that in the solid state, due to changes in the distribution of encapsulated water molecules. The relative stabilities in water of the seven complexes encapsulating various di- or tricarboxylate guests, either rigid or non-rigid, have been determined. The stability scale obtained for the dianionic complexes is interpreted in relation with the rigidity or flexibility of the guests. A DFT study demonstrates that additional stabilization arises from the presence of inner hydrogen bonds involving 1, 2 or 3 water molecules, which even permit the extension of the H-bonds network to the first solvation sphere of the anion. DFT calculations were carried out on all investigated complexes as isolated or solvated anions and provide the sequence of the bond energies between the host and the guests, which is compared to the experimental data. © 2008 The Royal Society of Chemistry.
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页码：4565 / 4574
页数：9
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