Inorganic Chemistry
ARTICLE
room temperature (Figure 5): 1 and 3 give a near-white photo-
luminescence emission when excited at 365 nm; an orange emission
is at variance observed when 4 is irradiated at 254 nm. When
irradiated at 365 nm, the Zn(II) derivative 1 gives a single, broad
emission band in the near-UV region, its maximum lying at
380 nm. When excited at 254 nm, the Cd(II) homologous 3 gives
two broad and partially superimposed emission bands with
maxima at 353 and 378 nm. Finally, when excited at 400 nm,
the Cu(I) species 4 gives one broad band in the visible region,
with maximum at 597 nm. The high-energy emissions shown by
1 and 3 may be confidently attributed to ligand-based [πꢀπ*]
excited states,37 with no involvement of the metal centers. On the
contrary, the low-energy photoluminescence emission of 4 is
reasonably due to a metal-to-ligand charge transfer (MLCT)
excited state, as is typical for Cu(I) complexes, in which the
ligand LUMO orbitals are sufficiently low in energy to accept an
excited electron from the electron-rich metal center.38
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4. CONCLUSIONS
The four coordination compounds Mx(BDMPX) (x = 1 for
M = Zn, 1; Co, 2; Cd, 3; x = 2 for M = Cu, 4) were prepared
by solvothermal reactions involving the flexible, pyrazole-based,
1,4-bis((3,5-dimethyl-1H-pyrazol-4-yl)methyl)benzene ligand
(H2BDMPX) and were fully characterized. All of them possess a
high thermal robustness, as witnessed by their stability in air at
least up to 300 °C. The species 1ꢀ3 feature a closed-pore 3-D
network, in which rhombic motifs can be recognized. Interest-
ingly, a certain framework flexibility toward an open-pore form is
brought about, in the case of 1 and 2, by N2 adsorption at 77 K.
Thus, 1 and 2 are a notable example of pro-porous materials,
their adsorption performances implying a low-temperature open-
ing of the rhombic motifs, stimulated by the gas probe and
facilitated by the nature of the ligand.
’ ASSOCIATED CONTENT
S
Supporting Information. Details on the synthesis of
b
H2BDMPX. IR spectroscopy for H2BDMPX and for species
1
1ꢀ4, H NMR for H2BDMPX. Rietveld refinement plots for
H2BDMPX, 1, and 3. TXRPD traces for 2 and 3. TXRPD data
treatment for 3. Comparative structural analysis of molecular
conformations in H2BDMPX and in 1ꢀ3. Crystallographic data
for species 1ꢀ3 in CIF format. This material is available free of
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: aurel.tabacaru@unicam.it (A.T.), simona.galli@uninsubria.it
(S.G.).
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2010, 3, 117–123.
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G.; Seyyedi, B.; Lamberti, C.; Bordiga, S. J. Am. Chem. Soc. 2010,
132, 7902–7904.
(16) Colombo, V.; Galli, S.; Choi, H. J.; Han, G. D.; Maspero, A.;
Palmisano, G.; Masciocchi, N.; Long, J. R. Chem. Sci. 2011, 2,
1311–1319.
’ ACKNOWLEDGMENT
Special thanks are addressed to Dr. Ivan Timokhin and Dr.
Stefano Lancianesi for sharing useful ideas, as well as to University
of Camerino (UNICAM) for funding.
’ REFERENCES
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