Tuning the thermodynamic stability of oxothiomolybdenum wheels

Crystal structures, studies in solution and DFT calculations

Jean François Lemonnier, Ali Kachmar, Sébastien Floquet, Jérôme Marrot, Marie Madeleine Rohmer, Marc Bénard, Emmanuel Cadot

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

The complexes [Mo12O12S12(OH)12(Muco)]2− (Muco2− = muconate, C6H4O4 2−) and [Mo12O12S12(OH)12(TMT)]2− (TMT2− = tetramethylterephthalate, C12H12O4 2−) 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 D2O 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.

Original languageEnglish
Pages (from-to)4565-4574
Number of pages10
JournalJournal of the Chemical Society. Dalton Transactions
Issue number34
DOIs
Publication statusPublished - 12 Jun 2008
Externally publishedYes

Fingerprint

Discrete Fourier transforms
Wheels
Thermodynamic stability
Tuning
Crystal structure
Water
Anions
Molecules
Solvation
Dimethyl Sulfoxide
Rigidity
Condensation
Hydrogen bonds
Stabilization
Nuclear magnetic resonance

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Tuning the thermodynamic stability of oxothiomolybdenum wheels : Crystal structures, studies in solution and DFT calculations. / Lemonnier, Jean François; Kachmar, Ali; Floquet, Sébastien; Marrot, Jérôme; Rohmer, Marie Madeleine; Bénard, Marc; Cadot, Emmanuel.

In: Journal of the Chemical Society. Dalton Transactions, No. 34, 12.06.2008, p. 4565-4574.

Research output: Contribution to journalArticle

Lemonnier, Jean François ; Kachmar, Ali ; Floquet, Sébastien ; Marrot, Jérôme ; Rohmer, Marie Madeleine ; Bénard, Marc ; Cadot, Emmanuel. / Tuning the thermodynamic stability of oxothiomolybdenum wheels : Crystal structures, studies in solution and DFT calculations. In: Journal of the Chemical Society. Dalton Transactions. 2008 ; No. 34. pp. 4565-4574.
@article{b435bd22b0244065b89bcfdd3e5eddc2,
title = "Tuning the thermodynamic stability of oxothiomolybdenum wheels: Crystal structures, studies in solution and DFT calculations",
abstract = "The complexes [Mo12O12S12(OH)12(Muco)]2− (Muco2− = muconate, C6H4O4 2−) and [Mo12O12S12(OH)12(TMT)]2− (TMT2− = tetramethylterephthalate, C12H12O4 2−) 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 D2O 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.",
author = "Lemonnier, {Jean Fran{\cc}ois} and Ali Kachmar and S{\'e}bastien Floquet and J{\'e}r{\^o}me Marrot and Rohmer, {Marie Madeleine} and Marc B{\'e}nard and Emmanuel Cadot",
year = "2008",
month = "6",
day = "12",
doi = "10.1039/b801716f",
language = "English",
pages = "4565--4574",
journal = "Dalton Transactions",
issn = "1472-7773",
publisher = "Royal Society of Chemistry",
number = "34",

}

TY - JOUR

T1 - Tuning the thermodynamic stability of oxothiomolybdenum wheels

T2 - Crystal structures, studies in solution and DFT calculations

AU - Lemonnier, Jean François

AU - Kachmar, Ali

AU - Floquet, Sébastien

AU - Marrot, Jérôme

AU - Rohmer, Marie Madeleine

AU - Bénard, Marc

AU - Cadot, Emmanuel

PY - 2008/6/12

Y1 - 2008/6/12

N2 - The complexes [Mo12O12S12(OH)12(Muco)]2− (Muco2− = muconate, C6H4O4 2−) and [Mo12O12S12(OH)12(TMT)]2− (TMT2− = tetramethylterephthalate, C12H12O4 2−) 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 D2O 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.

AB - The complexes [Mo12O12S12(OH)12(Muco)]2− (Muco2− = muconate, C6H4O4 2−) and [Mo12O12S12(OH)12(TMT)]2− (TMT2− = tetramethylterephthalate, C12H12O4 2−) 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 D2O 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.

UR - http://www.scopus.com/inward/record.url?scp=85034327359&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85034327359&partnerID=8YFLogxK

U2 - 10.1039/b801716f

DO - 10.1039/b801716f

M3 - Article

SP - 4565

EP - 4574

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1472-7773

IS - 34

ER -