Dalton Transactions
Paper
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Scheme 1 Esterification of phosphoric acid with equimolar lauryl
alcohol into MAP.
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mixture was diluted with water (5 mL) and isopropanol (5 mL),
transferred into a separating funnel and allowed to settle for
one hour. The supernatant oil layer was then separated directly
from the mixture and evaporated on a rotary evaporator at
90 °C until dry. The yield and selectivity of mono-dodecyl
phosphate (MAP) in the product mixture were determined by
potentiometric titration based on the amount of phosphoric
acid in the starting reactants with the three different dis-
sociation constants of H3PO4.31,32
Our experimental results show that a high yield of 88.5%
and selectivity of 93.8% for mono-dodecyl phosphate was
achieved with toluene as the dehydrant when the direct esteri-
fication of phosphoric acid with lauryl alcohol was carried out
at 110 °C for 24 h under the optimum catalyst dosage of 0.5%
(mass fraction). The above catalytic result is comparable with
other inorganic–organic compounds based on polyanions.32,33
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D. W. Lewis, A. Gómez, B. Nohra, P. Mialane, J. Marrot,
F. Sécheresse, C. Mellot-Draznieks, R. N. Biboum, B. Keita,
L. Nadjo and A. Dolbecq, J. Am. Chem. Soc., 2009, 131,
16078.
18 L. M. Rodriguez-Albelo, A. R. Ruiz-Salvador, D. L. Lewis,
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Conclusions
The 1D structure of ε(pyim)2 is built up of {PMoV8MoVI4O38-
(OH)2Zn4} units modified by pyim organic ligands. To the best
of our knowledge, ε2(pyim)6 is the first isolated structural com-
pound of dimeric ε-Zn POMs, with good electrochemical pro-
perties, and high catalytic activity in esterification, constructed
of eight-reduced ε-Keggin cores. The different structures of
ε(pyim)2 and ε2(pyim)6 demonstrate that slight changes of the
pH in the synthesis conditions can lead to a large difference in
the structures of the compounds you obtain. The luminescent
and electrochemical properties indicate that ε(pyim)2 and
ε2(pyim)6 have a wide range of potential applications in, e.g.,
photo or electrocatalysis. In addition, obtaining ε(pyim)2 and
ε2(pyim)6 based on the pyim ligand is an encouraging step
towards the synthesis of a new family of POMOFs linked by
pyim ligands.
19 B. Nohra, H. El-Moll, L. M. Rodriguez-Albelo, P. Mialane,
J. Marrot, C. Mellot-Draznieks, M. O’Keeffe, R. Ngo
Biboum, J. Lemaire, B. Keita, L. Nadjo and A. Dolbecq,
J. Am. Chem. Soc., 2011, 133, 13363.
20 L. M. Rodriguez-Albelo, G. Rousseau, P. Mialane, J. Marrot,
C. Mellot-Draznieks, A. R. Ruiz-Salvador, S. W. Li, R. J. Liu,
G. J. Zhang, B. Keita and A. Dolbecq, Dalton Trans., 2012,
41, 9989.
21 P. Mialane, A. Dolbecq and F. Sécheresse, Chem. Commun.,
2006, 3477.
Acknowledgements
This work was supported by the Natural Science Foundation of
Jiangsu province (BK2012823), the Qing Lan project and the
Project of Priority Academic Program Development of Jiangsu
Higher Education Institutions (PAPD).
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