Journal of the American Chemical Society
ARTICLE
conditions. Structures containing As(O,F) tetrahedra linked
’ REFERENCES
4
with M(O,F) polyhedra can also be produced either as new
topologies or as analogues of many of the compounds pre-
sented in Table 1.
n
(1) Natarajan, S.; Mandak, S. Angew. Chem., Int. Ed. 2008, 47, 4798.
(2) Barrer, R. M. Hydrothermal Chemistry of Zeolites; Academic
Press: London, 1982.
Advantages of fluoride-rich hydrofluorothermal synthesis in-
clude the ability to stabilize more unusual oxidation states in the
products, for example Mn(III) from the commercially available
(3) Wilson, S. T.; Lok, B. M.; Mesina, C. A.; Cannan, T. R.; Flanigen,
E. D. J. Am. Chem. Soc. 1982, 104, 1146.
(
4) Clearfield, A. Curr. Opin. Solid State Mater. Sci. 1996, 1, 268 and
references therein.
5) Cheetham, A. K.; F ꢀe rey, G.; Loiseau, T. Angew. Chem., Int. Ed.
999, 38, 3268.
6) Padhi, A. K.; Nanjundaswamy, K. S.; Goodenough, J. B. Electro-
MnF , though perhaps more important is that the route allows
3
(
facile and relatively safe (compared with the use of high
concentrations of HF) incorporation of high levels of fluoride
into the products, which as a result then contain species such as
1
(
chem. Soc. Meet. Abstr. 1996, 96ꢀ1, 73.
[
MO F ] and [PO F ]. The linking of these fluoride-rich poly-
3 3 2 2
(7) Hagman, L. O.; Kierkegaard, P. Acta Chem. Scand. 1968,
2, 1822.Boilot, J. P., Collin, G.; Colomban, P. Energy, Mines and
Resources; Natural Resources Canada: Ontario, Canada, CANMET
ERP/MSL 83-94(TR), 1983, 91.
hedra is markedly different from pure oxo-polyhedra leading to
new structural motifs such as channels and interlayer regions
lined with fluoride ions, low-dimensional metal centered chains,
and bridging fluoride between metal centers. Using the hydro-
fluorothermal methodology described herein, additional struc-
tural and compositional flexibility now exists for key transitional
metals such as Mn(III), Fe(III), Co(II), and Cu(II) whose
compounds have widespread applications in energy storage
devices, magnetic materials, and in catalysis.
(8) Rocha, J.; Lin, Z. Rev. Miner. Geochem. 2005, 57, 173. Nyman, M.;
Gu, B. X.; Wang, L. M.; Ewing, R. C.; Nenoff, T. M. Microporous
Mesoporous Mater. 2000, 40, 115.
(
(
(
9) Clearfield, A.; Thakur, D. S. Appl. Catal. 1986, 26, 1.
10) Ellis, B. L.; Lee., K. T.; Nazar, L. F. Chem. Mater. 2010, 22, 691.
11) Barker, J.; Saidi, M. Y.; Swoyer, J. L. Electrochem. Solid-State Lett.
2
003, 6, A1.
12) Ellis, B. L.; Makahnouk, W. R. M.; Makimura, Y.; Toghill, K.;
Nazar, L. F. Nat. Mater. 2007, 6, 749.
13) Barker, J.; Gover, R. K. B.; Burns, P.; Bryan, A. J. Electrochem.
(
’
ASSOCIATED CONTENT
(
S
Supporting Information. (1) Synthesis conditions and
Solid-State Lett. 2006, 9, A190. Kirsch, J. E.; Izumi, H. K.; Stern, C. L.;
Poeppelmeier, K. R. Inorg. Chem. 2005, 44, 4586.
b
experimental methods: (a) generic synthesis methods for transi-
tion metal fluorophosphates; (b) detailed synthesis parameters
for JMN10, CsMnF PO F; (c) detailed synthesis parameters for
(14) Dance, J.-M. Tressaud, A. Inorganic Solid Fluorides: Chemistry
and Physics; Hagenmuller, P. Ed.; Academic Press: Orlando, FL, 1985;
2
3
Chapter 9.
::
JCO140, [H ꢀN-(2-aminoethyl)-1,3-propane-diamine] [Co(II)-
2
2
(15) Murthy, J. K.; Gross, U.; R €u diger, S.; Unveren, E.; Kemnitz, E.
(
PO F)] F[PO F ] .(H O,F); (d) experimental methods and
3 4 2 2 2 2
J. Fluorine Chem. 2004, 125, 937.
instrumentation. (2) Thermogravimetric/differential thermal
analysis data for representative compounds. (3) SEM images
and EDAX data for representative compounds. (4) Li-ion
exchange of CsMnF PO F (JMN10), powder X-ray diffraction
(16) Rouse, J.; Redrup, K. V.; Kotsapa, E.; Weller, M. T. Chem.
Commun. 2009, 46, 7209.
(17) Bonhomme, F.; Thoma, S. G.; Rodriguez, M. A.; Nenoff, T. M.
Chem. Mater. 2001, 13 (6), 2112–2117. Lakiss, L.; Simon-Masseron, A.;
Porcher, F.; Patarin, J. Eur. J. Inorg. Chem. 2006, 237–243. Estermann,
M.; McCusker, L. B.; Baerlocher, Ch.; Merrouche, A.; Kessler, H. Nature
2
3
patterns before and after exchange, SEM images/EDAX data
before and after exchange. (5) Cyclic voltammogram for
discharge of Li into JFE31 CsFe(III)F (PO F)/carbon black.
1
991, 352, 320. F ꢀe rey, G. J. Fluorine Chem. 1995, 72, 187.
18) Riou-Cavellec, M.; Riou, D.; F ꢀe rey, G. Inorg. Chem. Acta 1999,
91, 317. Riou-Cavellec, M.; Gren ꢁe che, J.-M.; F ꢀe rey, G. J. Solid State
2
3
(
(
(
6) CIFs for metal fluorophosphates 1ꢀ8. (1) (NH ) Fe-
4
3
2
III) F (PO ) (Table 1, compound JFE32). (2) (CH NH )-
4 9 4 2 3 3
Chem. 1999, 148, 150.
(19) Adil, K.; Leblanc, M.; Maisonneuve, V.; Lightfoot, P. Dalton
Trans. 2010, 39, 5983.
(20) Sauvage, F.; Bodenez, V.; Vezin, H.; Albrecht, T. A.; Tarascon,
J.-M.; Poeppelmeier., K. R. Inorg. Chem. 2008, 47 (19), 8464.
(21) Tajimi, S.; Ikeda, Y.; Uematsu, K.; Toda, K.; Sato, M. Solid State
Ionics 2004, 175, 287.
FeFPO (Table 1, compound JFE123). (3) (NH )(Co(II) F -
4
4
3
2
(
P O F) ) (Table 1, compound JCO152). (4) [H ꢀN-(2-
2
6
2
2
aminoethyl)-1,3-propane-diamine]2 {[Co(II)(PO F)] F[PO -
3 4 2
F ] .(H O,F)} (Table 1, JCO140). (5) (NH )(MnF PO F)
2
2
2
4
2
3
(
Table 1, compound JMN16). (6) Na Mn F (P O ) (Table 1,
4 2 6 2 7
compound JMNJ15). (7) MCu (PO F )(PO F) F , M = K, Rb
3
2
2
3
2 2
(22) Armstrong, A. R.; Bruce, P. G. Nature 1996, 381, 499.
(Table 1 compounds ECU 230 and ECU 228). (8) M2-
(23) Removic-Langer, K.; Haussuhl, E.; Wichl, L.; Wolf, B.; Sauli, F.;
Cu P O F (Table 1 M = [NH ], ECU31; M = Rb
3
4
12
4
4
Hasselmann, N.; Kopietz, P.; Lang, M. J. Phys. Condens. Mater. 2009,
ECU261. This material is available free of charge via the
Internet at http://pubs.acs.org.
2
1
1
1, 185013.
24) Chung, S.-Y.; Bloking, J. T.; Chiang, Y. M. Nat. Mater. 2002,
, 123.
(25) Feng, P.; Bu, X.; Tolbert, S. H.; Stucky, G. D. J. Am. Chem. Soc.
997, 119, 2497.
26) El Khayati, N.; Cherkaoui El Moursli, R.; Rodriguez-Carvajal, J.;
(
’
AUTHOR INFORMATION
Corresponding Author
(
Andre, G.; Blanchard, N.; Bouree, F.; Collin, G.; Roisnel, T. Euro. Phys. J.
B. 2001, 22, 429.
(
27) Yakubovich, O. V.; Simonov, M. A.; Matvienko, E. N.; Belov,
N. V. Doklady Akademii Nauk SSSR. 1978, 238, 576.
28) Sauvage, F.; Quarez, E.; Tarascon, J. M.; Baudrin, E. Solid State
Sci. 2006, 8, 1215.
’
ACKNOWLEDGMENT
(
We thank EPSRC for allied funding under EP/F013752/1,
John Owen and Matthew Roberts for the preliminary electro-
chemical measurements, Edward Young for the collection of the
magnetic susceptibility data, and Mark Light for assistance with
some aspects of the structure solution from single crystal data.
8
263
dx.doi.org/10.1021/ja201096b |J. Am. Chem. Soc. 2011, 133, 8252–8263