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The electronegativity of sulfur is different in SO2, where S is in
the formal +4 oxidation state compared with H2S, where it is in
the -2 oxidation state. This has some influence on the
coordination of the two gases to the ring; the shortest S…F
contacts in SO2@Cr8 is 3.326(3) while in H2S@Cr8 it is 3.667(1)
Å. Both contacts are longer than the sum of the Van der Waals
radii, but it appears the interaction is stronger in the former
adduct. This is also borne out by relative binding energies,
which we measure at around 25 kJ mol-1 for binding SO2 in
SO2@Cr8 compared with 14 kJ mol-1 binding of H2S in H2S@Cr8.
DOI: 10.1039/C9DT02378J
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Capturing of SO2 and H2S molecules by a Cr8 metallacrown
occurs with no loss of crystallinity thus allowing us to perform
single X-ray diffraction experiments as a method to study gas
release. Upon heating the loaded metallacrowns, the molecules
are released, demonstrating a reversible process. This is the first
example of a metallacrown adsorbing such molecules.
There are aspects of these results that will be investigated
further. The Cr8 metallacrown has been studied almost
exclusively with pivalate as the carboxylate.24-28 The
heterometallic versions of this ring {Cr7M} (where M = a divalent
metal) is known with many carboxylates.48 Preparing Cr8 rings
with other carboxylates might produce molecules where SO2
could further into the core of the ring.
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Conflicts of interest
There are no conflicts to declare.
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D.F.S thanks the University of Manchester for a President’s
Doctoral Scholarship. We acknowledge financial support from
the EPSRC (grant references EP/R03480X/1 and EP/P002560/1)
and for funding an X-ray diffractometer (EP/K039547/1). We
thank Martin Jennings and Anne Davies for the help provided
in the elemental analysis TGA, and DSC measurements. We
also thank Dr Joe McDouall for helpful discussions. D. R.
acknowledge the provision of CPU time on the Computational
Shared Facility at the University of Manchester.
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