Inorganic Chemistry
Article
supported by JSPS KAKENHI Grant Number JP16K06863.
We thank T. Amimoto and N. Kawata at the Natural Science
Center for Basic Research and Development (N-BARD),
Hiroshima University, for the ESI-MS measurement and initial
single crystal X-ray structure analysis, respectively.
with a 5-fold Symmetry: The Series [LnP
5
W
30
O
110]12‑ (Ln3+ = Tb, Dy,
Ho, Er, Tm, and Yb). J. Am. Chem. Soc. 2012, 134, 14982−14990.
18) Fernandez, J. A.; Lopez, X.; Bo, C.; de Graaf, C.; Baerends, E. J.;
Poblet, J. M. Polyoxometaltes with Internal Cavities: Redox Activity,
(
́
́
n+
(15‑n)‑
Basicity and Cation Encapsulation in [X P W O110]
Preyssler
5
30
3+
+
2+
3+
3+
4+
Complexes, with X = Na , Ca , Y , La , Ce , and Th . J. Am.
Chem. Soc. 2007, 129, 12244−12253.
REFERENCES
(19) Antonio, M. R.; Soderholm, L. Implications of the unusual redox
■
1
2‑
behavior exhibited by the heteropolyanion [EuP W O ] . J. Alloys
5
30 110
(
1) Pope, M. T. Heteropoly and Isopoly Oxometalates; Springer-
Verlag: Berlin, 1983.
Compd. 1997, 250, 541−543.
20) Soderholm, L.; Liu, G. K.; Muntean, J.; Malinsky, J.; Antonio, M.
R. Coordination and Valence of Europium in the Heteropolyanion
(
(
9
(
2
2) Hill, C. L. Thematic issue on Polyoxometalates. Chem. Rev. 1998,
8, 1−390.
3) Cronin, L. Thematic Issue on Polyoxometalates. Chem. Soc. Rev.
012, 41, 7325−7648.
4) Alizadeh, M. H.; Harmalker, S. P.; Jeannin, Y.; Martin-Frer
1
2‑
[
EuP W O ] . J. Phys. Chem. 1995, 99, 9611−9616.
5
30 110
(
21) Antonio, M. R.; Soderholm, L. Redox Behavior of Europium in
1
2‑
the Preyssler Heteropolyanion [EuP W O ] . J. Cluster Sci. 1996,
(
̀
e, J.;
5
30 110
7
(
, 585−591.
Pope, M. T. A Heteropolyanion with Fivefold Molecular Symmetry
That Contains a Nonlabile Encapsulated Sodium Ion. The Structure
and Chemistry of [NaP W O ] . J. Am. Chem. Soc. 1985, 107,
22) Antonio, M. R.; Soderholm, L.; Williams, C. W.; Ullah, N.;
14‑
Francesconi, L. C. Redox behavior of cerium in heteropolyoxotung-
5
30 110
state complexes. J. Chem. Soc., Dalton Trans. 1999, 3825−3830.
2
(
662−2669.
(23) Chiang, M.-H.; Antonio, M. R.; Soderholm, L. Energetics of the
5) Creaser, I.; Heckel, M. C.; Neitz, R. J.; Pope, M. T. Rigid
(15‑n)‑
Preyssler anion’s molecular orbitals: quantifying the effect of the
encapsulated-cation’s charge. Dalton Trans. 2004, 3562−3567.
Nonlabile Polyoxometalate Cryptates [ZP W O110]
That Exhibit
5
30
Unprecedented Selectivity for Certain Lanthanide and Other Multi-
(24) Zhang, Z.-M.; Yao, S.; Li, Y.-G.; Han, X.-B.; Su, Z.-M.; Wang, Z.-
valent Cations. Inorg. Chem. 1993, 32, 1573−1578.
S.; Wang, E.-B. Inorganic Crown Ethers: Sulfate-Based Preyssler
(
6) Liang, M.-X.; Ruan, C.-Z.; Sun, D.; Kong, X.-J.; Ren, Y.-P.; Long,
Polyoxometalates. Chem. - Eur. J. 2012, 18, 9184−9188.
L.-S.; Huang, R.-B.; Zhen, L.-S. Solvothermal Synthesis of Four
Polyoxometalate-Based Coordination Polymer Including Diverse
Ag(I)-π Interactions. Inorg. Chem. 2014, 53, 897−902.
(25) Sadakane, M.; Ichi, Y.; Ide, Y.; Sano, T. Thermal Stability and
Acidic Strength of Preyssler-Type Phosphotungstic Acid,
H [P W O110Na] and It’s Catalytic Activity for Hydrolysis of Alkyl
(
7) Hu, T.-P.; Zhao, Y.-Q.; Jaglicic, Z.; Yu, K.; Wang, X.-P.; Sun, D.
14
5
30
Acetates. Z. Anorg. Allg. Chem. 2011, 637, 2120−2124.
Four Hybrid Materials Based on Preyssler P5W30 Polyoxometalate
and Frist-Row Transition-Metal Complex. Inorg. Chem. 2015, 54,
(26) Burla, M. C.; Caliandro, R.; Camalli, M.; Carrozzini, B.;
Cascarano, G. L.; Giacovazzo, C.; Mallamo, M.; Mazzone, A.; Polidori,
G.; Spagna, R. SIR2011: a new package for crystal structure
determination and refinement. J. Appl. Crystallogr. 2012, 45, 357−361.
7
(
415−7423.
8) Zhao, Y.-Q.; Yu, K.; Wang, L.-W.; Wang, Y.; Wang, X.-P.; Sun, D.
Anion-Induced Supramolecular Isomerization in Two Preyssler
P5W30 Polyoxometalate-Based Hybrid Materials. Inorg. Chem. 2014,
(27) Sheldrick, G. M. A short history of SHELX. Acta Crystallogr.,
Sect. A: Found. Crystallogr. 2008, A64, 112−122.
5
(
3, 11046−11050.
9) Dickman, M. H.; Gama, G. J.; Kim, K.-C.; Pope, M. T. The
Structure of Europium(III)- and Uranium(IV) Derivatives of
(28) van der Sluis, P.; Spek, A. L. BYPASS: an effective method for
the refinement of crystal structures containing disordered solvent
regions. Acta Crystallogr., Sect. A: Found. Crystallogr. 1990, 46, 194−
201.
(29) Fonseca Guerra, C.; Snijders, J. G.; Te Velde, G.; Baerends, E. J.
Towards an order-N DFT method. Theor. Chem. Acc. 1998, 99, 391−
403.
(30) Te Velde, G.; Bickelhaupt, F. M.; van Gisbergen, S. J. A.;
Fonseca Guerra, C.; Baerends, E. J.; Snijders, J. G.; Ziegler, T.
Chemistry with ADF. J. Comput. Chem. 2001, 22, 931−967.
(31) Optimized structures must be very accurate when frequency
calculations are to be conducted, since molecular vibrations can be
highly dependent on geometrical parameters.
15‑
[
7
P W O ] : Evidence for ″Cryptohydration″. J. Cluster Sci. 1996,
5
30 110
, 567−583.
(
10) Williams, C. W.; Antonio, M. R.; Soderholm, L. The formation
12‑
12‑
and stability of [EuP W O110] and [AmP W O ] . J. Alloys
5
30
5
30 110
Compd. 2000, 303−304, 509−513.
(
11) Antonio, M. R.; Soderholm, L. Cerium Valence in Cerium-
Exchanged Preyssler’s Heteropolyanion through X-ray Absorption
Near-Edge Structure. Inorg. Chem. 1994, 33, 5988−5993.
(
12) Granadeiro, C. M.; de Castro, B.; Balula, S. S.; Cunha-Silva, L.
Lanthanopolyoxometalates: From the structure of polyanions to the
design of functional materials. Polyhedron 2013, 52, 10−24.
(
13) Takahashi, K.; Sano, T.; Sadakane, M. Preparation and
(32) Handy, N. C.; Cohen, A. J. Left-right correlation energy. Mol.
characterization of Preyssler-type phosphotungstic acid,
Phys. 2001, 99, 403−412.
n+
H15‑n[P W O M ], with different encapsulated cations (M = Na,
(33) Swart, M.; Ehler, A. W.; Lammertsma, K. Performance of the
OPBE exchange-correlation functional. Mol. Phys. 2004, 102, 2467−
2474.
5
30 110
Ca, Bi, Eu, Y, or Ce), and their thermal stability and acid catalyst
properties. Z. Anorg. Allg. Chem. 2014, 640, 1314−1321.
(
14) Kim, K.-C.; Pope, M. T.; Gama, G. J.; Dickman, M. H. Slow
̈ ̈
(34) Klamt, A.; Schuurmann, G. COSMO: a new approach to
Proton Exchange in Aqueous Solution. Consequences of Protonation
and Hydration within the Central Cavity of Preyssler Anion
dielectric screening in solvents with explicit expressions for the
screening energy and its gradient. J. Chem. Soc., Perkin Trans. 2 1993, 2,
799−805.
n‑
Derivatives, [|M(H O)|P W O ] . J. Am. Chem. Soc. 1999, 121,
2
5
30 110
1
(
1164−11170.
15) Hayashi, A.; Haioka, T.; Takahashi, K.; Bassil, B. S.; Kortz, U.;
Sano, T.; Sadakane, M. Cation effect on formation of Preyssler-type
0-tungsto-5-phosphate: enhanced yield of Na-encapsulated derivative
̈
(35) Andzelm, J.; Kolmel, C.; Klamt, A. Incorporation of solvent
effects into density functional calculations of molecular energies and
geometries. J. Chem. Phys. 1995, 103, 9312−20.
3
(36) Klamt, A. Conductor-like Screening Model for Real Solvents: A
New Approach to the Quantitative Calculation of Solvation
Phenomena. J. Phys. Chem. 1995, 99, 2224−35.
and direct synthesis of Ca- and Bi-encapsulated derivatives. Z. Anorg.
Allg. Chem. 2015, 641, 2670−2676.
(
16) Antonio, M. R.; Chiang, M.-H. Stabilization of Plutonium(III)
(37) Pye, C. C.; Ziegler, T. An implementation of the condutor-like
screening model of solvation within the Amsterdam density functional
package. Theor. Chem. Acc. 1999, 101, 396−408.
(38) Bersuker, I. The Jahn Teller Effect; Cambridge University Press:
Cambridge, 2006.
in the Preyssler Polyoxometalate. Inorg. Chem. 2008, 47, 8278−8285.
(
17) Cardona-Serra, S.; Clemente-Juan, J. M.; Coronado, E.; Gaita-
Arino, A.; Camon, A.; Evangelisti, M.; Luis, F.; Martines-Perez, M. J.;
Sere, J. Lanthanoid Single-Ion Magnets Based on Polyoxometalates
I
Inorg. Chem. XXXX, XXX, XXX−XXX