Inorganic Chemistry
Communication
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Table 1. Comparison between Calculated and Experimental
UO Lengths for the Synthesized Uranyl Diphosphonates
2+
ν3 of UO2
Bartlett’s
law (pm)
Veal’s law
(pm)
12184.
(cm−1
)
exptl (pm)
180.7
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B.; Zhang, X. X.; Xu, B. J. Am. Chem. Soc. 2006, 128, 13358. (b) Yang, Z.
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Sun, Z. M. Cryst. Growth Des. 2012, 12, 4669.
ZnUEDP
ZnUPDP
880
897
852
896
927
866
927
942
179.9
178.7
182.1
178.7
176.5
181.0
176.5
175.5
177.9
176.8
179.9
176.9
175.0
178.9
175.0
174.0
178.5
183.2
177.4
176.1
ZnUBDP
180/179.5
176.1
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Inorg. Chem. 2013, 52, 2736.
175.5/175.4/174.7
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Alekseev, E. V.; Jouffret, L. J.; Depmeier, W.; Albrecht-Schmitt, T. E.
complexes exhibit typical green light ranging from 480 to 580 nm
with well-structured emission bands (480, 496, 506, 517, 528,
539, 551, and 564 nm for ZnUEDP, 510, 531, and 554 nm for
ZnUPDP, and 486, 503, 524, 547, and 572 nm for ZnUBDP).
These emission peaks are related to the symmetric and
antisymmetric vibrational modes of the uranyl cation.
In summary, we have synthesized the first examples of uranyl
phosphonates with heterometallic UVIOZnII CCIs. These
compounds are constructed of flexible alkyl-based diphospho-
nate ligands. With an increase in the alkyl chain, the framework
structure of ZnUBDP is formed, instead of layered assemblies of
ZnUEDP and ZnUPDP. This work demonstrates that uranyl
phosphonates with novel structural arrangements will be
achieved by using flexible phosphonate ligands. Future work
will be focused on the expansion and modification of the
phosphonate ligands to isolate new uranyl complexes.
́
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E.; Yahia, A.; Maron, L.; Parsons, S.; Love, J. B. Nat. Chem. 2010, 2, 1056.
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Loiseau, T. Chem.Eur. J. 2013, 19, 2012.
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Yang, M.; Chen, J. S. J. Am. Chem. Soc. 2003, 125, 9266. (c) Tian, T.;
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(16) Synthesis details: A mixture of Zn(UO2)(OAc)4·7H2O (40 mg),
diphosphonic acid (40 mg), bipy (20 mg for ZnUEDP) or phen (20 mg
for ZnUPDP and ZnUBDP), and deionized water (3.0 mL) was loaded
into a 20-mL Teflon-lined stainless steel autoclave. The autoclave was
sealed and heated at 160 °C for 2 days and then cooled to room
temperature. Yellow blocklike crystals were isolated. Yield: 20 mg
(72.1% based on uranium) for ZnUEDP. Anal. Calcd for
C12H12N2O8P2UZn: C, 21.27; H, 1.79; N, 4.13. Found: C, 20.66; H,
1.75; N, 3.98. Yield: 18 mg (64.3% based on uranium) for ZnUPDP.
Anal. Calcd for C30H32N4O18P4U2Zn: C, 25.74; H, 2.16; N, 4.00. Found:
C, 25.81; H, 2.22; N, 4.09. Yield: 15 mg (59.8% based on uranium) for
ZnUBDP. Anal. Calcd for C20H16N2O20P4U3Zn: C, 15.93; H, 1.07; N,
1.86. Found: C, 15.87; H, 1.01; N, 1.83. Powder XRD has been
characterized to confirm the phase purity (Figure S11 in the SI), and
thermogravimetric analysis curves (Figure S12 in the SI) were used to
study the thermal stability and water content of the title compounds.
(17) (a) Burns, P. C.; Ewing, R. C.; Hawthorne, F. C. Can. Mineral.
1997, 35, 1551. (b) Brese, N. E.; O’Keeffe, M. Acta Crystallogr. 1991,
B47, 192.
ASSOCIATED CONTENT
* Supporting Information
■
S
Experimental details for phosphonic acids, X-ray crystallographic
files in CIF format (CCDC 931846−931848), crystal data and
structure refinement, selected bond length and angles, powder
XRD patterns, thermogravimentric analysis curves, structural
pictures, IR, Raman, UV−vis, and photoluminescent spectra for
all compounds. This material is available free of charge via the
AUTHOR INFORMATION
Corresponding Author
■
Author Contributions
‡These authors contributed equally.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
(18) (a) Veal, B. W.; Lam, D. J.; Carnall, W. T.; Hestra, H. R. Phys. Rev.
B 1975, 5651. (b) Bartlett, J. R.; Cooney, R. P. J. Mol. Struct. 1989, 193,
295.
We are thankful for support of this work by the National Nature
Science Foundation of China (Grants 21171662 and 21101148),
Jilin Province Youth Foundation (20130522132JH,
20130522123JH, and 201201005) and SRF for ROCS (State
Education Ministry).
REFERENCES
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dx.doi.org/10.1021/ic4009834 | Inorg. Chem. 2013, 52, 8288−8290