◦
recorded in a static atmosphere of nitrogen at a heating rate of 10
2 (a) S. Khanra, S. Konar, A. Clearfield, M. Helliwell, E. J. L. McInnes,
E. Tolis, F. Tuna and R. E. P. Winpenny, Inorg. Chem., 2009,
min- between 30–850 C. The compound 1 is stable up to 275 C
Fig. S15 in the ESI†) and showed sharp single-step decomposition
in the temperature range 230–340 C, assigned to the loss of the
1
◦
◦
4
8, 5338; (b) C. Lampropoulos, K. A. Abboud, T. C. Stamatatos
(
and G. Christou, Inorg. Chem., 2009, 48, 813; (c) A. Escuer, G.
Vlahopoulou, S. P. Perlepes and F. A. Mautner, Inorg. Chem., 2011, 50,
2468.
◦
four Schiff base fragments (~39.8% weight loss). For 2·2H
2
O (Fig.
◦
3 A. Volbeda, A. Lahm, F. Sakiyama and D. Suck, EMBO J., 1991, 10,
S15 in the ESI†) loss of water starts ~78.7 C and completes at
6.75 C. The observed loss of weight is 3.246%, which agrees well
1
607.
◦
9
4
(a) E. Hough, L. K. Hansen, B. Birkens, K. Jynes, S. Hansen, A.
with the calculated value of 4.2% for two water molecules.
Hordvik, C. Little, E. Dodson and Z. Derewenda, Nature, 1989, 338,
3
57; (b) S. K. Burley, P. R. David, R. M. Sweet, A. Tayler and W. N.
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X-Ray crystallography
5
6
(a) E. E. Kim and H. W Wyckoff, J. Mol. Biol., 1991, 218, 449; (b) A.
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J. Y. Koh, Annu. Rev. Neurosci., 1998, 21, 347.
The intensity data of the complexes 1 and 2·2H
2
O were collected
on a Nonius Kappa CCD and Bruker APEX-II CCD X-ray
diffractometer that uses graphite-monochromated Mo-Ka radi-
ation (l = 0.71073 A) at 293 K, using single crystals. Information
concerning the X-ray data collection and structure refinement of
the compound is summarized in Table 1. For complex 1, a total of
˚
7
M. Fondo, N. Ocampo, A. M. Garca-Deibe and J. Sanmartin, Inorg.
Chem., 2009, 48, 4971.
3208 reflections were recorded with Miller indices hmin = -15, hmax
=
8 (a) J. J. Danford, P. Dobrowolski and L. M. Berreau, Inorg. Chem.,
2
009, 48, 11352; (b) A. A. Russell, K. Doyle, A. M. Arif and L. M.
1
5, kmin = -22, kmax = 25, lmin = -17, lmax = 17. For complex 2·2H O,
2
Berreau, Inorg. Chem., 2006, 45, 4097.
L. A. Gavrilova and B. Bosnich, Chem. Rev., 2004, 104, 349.
a total of 4132 reflections were recorded with Miller indices hmin
=
9
-
31, hmax = 31, kmin = -14, kmax = 14, lmin = -20, lmax = 20. In the final
10 (a) D. Mandal and D. Ray, Inorg. Chem. Commun., 2007, 10, 1202;
(b) S. S. Tandon, D. S. Bunge, R. Rakosi, Z. Xu and L. K. Thompson,
Dalton Trans., 2009, 6536.
1 D. Mandal, V. Bertolasi, J. R. Ari n˜ o, G. Arom ´ı and D. Ray, Inorg.
Chem., 2008, 47, 3465.
2
cycles of full-matrix least squares on F all non-hydrogen atoms
were assigned anisotropic thermal parameters. The structures were
1
29
solved using SIR97 and SHELX-97 system of programmes.
1
1
2 N. L. William and S. Norbert, Chem. Rev., 1996, 96, 2375.
3 (a) T. K. Cole and R. G. Linck, Inorg. Chem., 1988, 27, 1498; (b) D. E.
Fogg and B. R. James, Inorg. Chem., 1995, 34, 2557.
Conclusions
1
4 A. Tamilselvi and M. Govindasamy, JBIC, J. Biol. Inorg. Chem., 2008,
We have investigated the fluorescence and binding behavior
1
3, 1039.
2
+
of H
selectivity for Zn in comparison to other metal ions and zinc
ion coordination selective fluorescence properties. With H bemp,
the neutral Zn nuclearity in the form of a compact triangle has
3
bemp and H
3
bpmp with Zn . In solution they indicate
15 R. S. Forgan, J. E. Davidson, S. G. Galbraith, D. K. Henderson,
2
+
Parsons, S. Parsons, P. A. Tasker and F. J. White, Chem. Commun.,
2
008, 4049.
3
1
1
1
6 R. R. Gagne, C. L. Spiro, T. J. Smith, C. A. Hamann, W. R. Thies and
A. K. Shiemke, J. Am. Chem. Soc., 1981, 103, 4073.
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Jiang, Chin. J. Chem., 1995, 13, 497.
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0 M.N. Burnett, C.K. Johnson, ORTEP III, Report ORNL-6895, Oak
Ridge National Laboratory, Oak Ridge, TN, 1996.
3
been achieved in 1 as a single crystalline end product by the
combined action of singly deprotonated parent H
hydrolyzed form emp . The combined effect of the two ligands,
one derived from the other, introduces phenoxido and alkoxido
bridging moieties. The fluorescent coordinative interaction of the
-
2
bemp and its
2
-
1
2
+
second ligand, also selective towards the Zn ion, instead leads to
O of two zwitterionic ligands.
2
the generation of mononuclear 2·2H
2
In addition, the trinuclear and mononuclear zinc(II) complexes
reported can function as precursors for the preparation of ZnO
nano structures.
21 A. R. Paital, V. Bertolasi, G. Arom ´ı , J. R. Ari n˜ o and D. Ray, Dalton
Trans., 2008, 861.
2
2
2 M. Prabhakar, P. S. Zacharias and S. K. Das, Inorg. Chem., 2005, 44,
585.
2
3 (a) C. L. Dollberg and C. Turro, Inorg. Chem., 2001, 40, 2484; (b) D.
M. Roundhill, Photochemistry and Photophysics of Metal Complexes,
J. P. Fackler, ed., Modern Inorganic Chemistry Series, Plenum Press,
New York, 1994, p 56.
Acknowledgements
A.S. is thankful to the University Grant Commission, New
Delhi, India for the research fellowship. The authors also give
thanks to DST, New Delhi, for providing the Single Crystal X-
ray Diffractometer facility in the Department of Chemistry, IIT
Kharagpur under its FIST program. V.B. acknowledeges Italian
Ministry of University and Scientific Research, MIUR, Rome,
Italy.
2
4 (a) A. Mallick and N. Chahattopadhyay, Photochem. Photobiol., 2005,
81, 419; (b) H. A. Benesi and J. H. Hildebrand, J. Am. Chem.
Soc., 1949, 71, 2703; (c) N. J. Turro, Modern Molecular Photochem-
istry, Benjamin Cummings Publishing Co., Inc., Menlo Park, CA,
1
978.
2
2
5 J. R. Lakowicz, Principles of Fluorescence Spectroscopy, 2nd ed.,
Kluwer Academic/Plenum, New York, 1999.
6 S. S. Tan, S. J. Kim and E. T. Kool, J. Am. Chem. Soc., 2011, 133,
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664.
2
2
2
7 S. Banthia and A. Samanta, J. Phys. Chem. B, 2002, 106, 5572.
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Giacovazzo, A. Guagliardi, A. G. Moliterni and R. J. Spagna, Appl.
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for Crystal Structure Refinement, University of G o¨ ttingen, Germany,
1997.
Notes and References
1
(a) M. Sarkar, R. Cl e´ rac, C. Mathoni e´ re, N. G. R. Hearns, V. Bertolasi
and D. Ray, Inorg. Chem., 2010, 49, 6575; (b) M. Sarkar, R. Cl e´ rac, C.
Mathoni e´ re, N. G. R. Hearns, V. Bertolasi and D. Ray, Inorg. Chem.,
2
011, 50, 3922.
1
896 | Dalton Trans., 2012, 41, 1889–1896
This journal is © The Royal Society of Chemistry 2012