Data di Pubblicazione:
2009
Citazione:
Molecular Iodine Stabilization in an Extended N···I–I···N Assembly / F. Isaia, M.C. Aragoni, M. Arca, F. Demartin,
F.A. Devillanova, G. Ennas, A. Garau, V. Lippolis, A. Mancini, G. Verani. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1434-1948. - :24(2009), pp. 3667-3672.
Abstract:
The adduct [bis(quinoxaline)-2,2 ,3,3 -disulfide·I2] (Q2S2·I2)
(1) can be easily synthesised from the reaction of Q2S2 and
I2 in CH2Cl2 or, in the absence of any solvent, through diffusion
of I2 vapours at 60 °C. X-ray diffraction analysis shows
the presence of an extended N···I–I···N assembly in which
each I2 molecule links a Q2S2 molecule at both ends through
a nitrogen atom to form a polymeric species; the d(I–I) and
d(N–I) bond lengths confirm a very weak nitrogen–iodine interaction
at the base of the N···I–I···N assembly. DFT calculations
provide optimised distances for the N···I and I–I bonds
and explanation for the zigzag chain formation: the
mPW1PW functional and the B3LYP hybrid functional with a variety of basis sets for the I atomic species [CRENBL,
LANL2DZ, LANL2DZ(d,p), LANL08(d), SBKJC, SBKJC polarised-
LFK and Stuttgart RLC] have been tested. Compound
1 proved stable up to nearly 100 °C, and the stability is to be
mainly attributed to the lattice energy of its polymeric structure
then to donor–acceptor stabilisation. The facile insertion
of molecular iodine into the Q2S2 network makes this compound
an interesting iodine sponge, suitable for I2 storage;
moreover, Q2S2 can easily collect and release I2(g) by a temperature-
controlled process (60 and 97 °C, respectively).
Tipologia IRIS:
01 - Articolo su periodico
Keywords:
Density functional calculations; Donor-acceptor systems; Iodine; N,S ligands; X-ray diffraction
Elenco autori:
F. Isaia, M.C. Aragoni, M. Arca, F. Demartin,
F.A. Devillanova, G. Ennas, A. Garau, V. Lippolis, A. Mancini, G. Verani
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