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netically coupled systems, where the diamagnetic correction is of
the same order of magnitude as the uncorrected molar susceptibil-
ity, the uncertainty of the corrected values is large. In view of this,
we decided to perform DFT theoretical calculations to evaluate the
magnetic exchange coupling constants and to check the experi-
mental values. The J values were obtained as the intrinsic energy
difference between the broken symmetry singlet state and the cor-
responding triplet state. The computed J values for 1–3 are given in
Table 4 and compare reasonably well with the experimental val-
ues. In view of the above results, it seems that in the case of strong
AF Cu2 coupled systems with J values smaller than ꢁ400 cm–1, the
fit of the magnetic data still leads to relatively accurate J values if
the diamagnetic correction is properly performed.
The spin density surfaces for 1–3 obtained from the broken
symmetry singlet state (the spin density of 1 is given as an exam-
ple in Fig. 8, whereas those for 2 and 3 are given as Supplementary
Material) clearly show that spin density at each copper(II) atom
has the shape of a dx
orbital and it is
r
delocalized on the donor
atoms directly attached to the metal. Therefore, exchange pathway
is of the type, involving the dx magnetic orbitals of the cop-
2ꢁy2
r
2ꢁy2
per(II) atoms and the p orbitals of the bridging oxygen atoms.
4. Conclusions
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The use of aromatic carboxylate anions in the synthesis of dinu-
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metal–organic frameworks. The structures of alkoxo-bridged dinu-
clear copper(II) complexes of the formula [Cu2(ap)2(L)2Sn]
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This work was supported by the Academy of Finland (project
119916, to R.S.), MEC (Spain) (project CTQ-2008-2269/BQU, E.C.
and A.J.M.) the Junta de Andalucía (FQM-195) and the University
of Granada (research contract to A.J.M.). The authors are grateful
to Elina Hautakangas for performing the elemental analyses and
to the Center of Supercomputation of the University of Granada
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Appendix A. Supplementary material
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CCDC 738527, 738528, 738529, 738530 contain the supplemen-
tary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
data associated with this article can be found, in the online version,
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